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Hierarchically Structured Zeolites: From Design to Application

Li-Hua Chen,* Ming-Hui Sun, Zhao Wang, Weimin Yang,* Zaiku Xie,* and Bao-Lian Su*

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ABSTRACT: Hierarchical zeolites combine the intrinsic catalytic properties of micro-

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porous zeolites and the enhanced access and transport of the additional meso- and/or
macroporous system. These materials are the most desirable catalysts and sorbents for
industry and become a highly evolving field of important current interests. In addition to the
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enhanced mass transfer leading to high activity, selectivity, and cycle time, another essential
merit of the hierarchical structure in zeolite materials is that it can significantly improve the
utilization effectiveness of zeolite materials resulting in the minimum energy, time, and raw
materials consumption. Substantial progress has been made in the synthesis, character-
ization, and application of hierarchical zeolites. Herein, we provide an overview of recent
achievements in the field, highlighting the significant progress in the past decade on the
development of novel and remarkable strategies to create an additional pore system in
zeolites. The most innovative synthesis approaches are reviewed according to the principle,
versatility, effectiveness, and degree of reality while establishing a firm link between the preparation route and the resultant
hierarchical pore quality in zeolites. Zeolites with different hierarchically porous structures, i.e., micro-mesoporous structure, micro-
macroporous structure, and micro-meso-macroporous structure, are then analyzed in detail with concrete examples to illustrate their
benefits and their fabrications. The significantly improved performances in catalytic, environmental, and biological applications
resulting from enhanced mass transport properties are discussed through a series of representative cases. In the concluding part, we
envision the emergence of “material-properties-by-quantitative and real rational design” based on the “generalized Murray’s Law”
that enables the predictable and controlled productions of bioinspired hierarchically structured zeolites. This Review is expected to
attract important interests from catalysis, separation, environment, advanced materials, and chemical engineering fields as well as
biomedicine for artificial organ and drug delivery systems.

CONTENTS 4.1.3. Fischer−Tropsch Synthesis Process AU

4.1.4. Hydroconversion Process AV
1. Introduction B 4.1.5. Oxidation Reaction AZ
2. Synthesis C 4.1.6. Transformation of Methanol BD
2.1. In Situ Approach D 4.1.7. Catalytic Cracking Reaction BH
2.1.1. Templating Route D 4.1.8. Biomass Conversion BM
2.1.2. Nontemplating Route X 4.1.9. Conclusion BP
2.2. Postsynthesis Approach AD 4.2. Environmental Applications BP
2.2.1. Demetalation AD 4.2.1. Wastewater Treatment BP
2.2.2. Delamination AG 4.2.2. Adsorptive Desulfurization BQ
2.2.3. Recrystallization AH 4.2.3. CO2 Capture BQ
3. Hierarchical Structure AI 4.2.4. Removal of Volatile Organic Com-
3.1. Micro-Mesoporous Structured Zeolites AK pounds BR
3.1.1. Disordered Micro-Mesoporous Struc- 4.3. Biological Applications BS
tured Zeolites AK 4.4. Conclusions BS
3.1.2. Ordered Micro-Mesoporous Structured 5. Conclusion and Future Trends BT
Zeolites AL
3.2. Micro-Macroporous Structured Zeolites AM
3.3. Micro-Meso-Macroporous Structured Zeo- Received: January 8, 2020
lites AM
4. Applications AO
4.1. Catalytic Application AO
4.1.1. Friedel−Crafts Reaction AO
4.1.2. Beckmann Rearrangement AT

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.chemrev.0c00016

A Chem. Rev. XXXX, XXX, XXX−XXX
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Author Information BV
Corresponding Authors BV
Authors BV
Notes BV
Biographies BV
Acknowledgments BV
References BV
1. INTRODUCTION
Zeolites are an important family of crystalline microporous
materials with three-dimensional framework constructed by
corner-sharing TO4 tetrahedrons (T refers to tetrahedrally
coordinated framework atoms Si, Al, or other heteroatoms).
The different ways of TO4 tetrahedra connections result in a
rich variety of zeolite microporous structures. These micro-
porous materials are either formed naturally by volcanic
activity or synthesized artificially in the laboratory. Currently,
245 distinct zeolite framework structures are recognized by the
Structure Commission of the International Zeolite Association
(IZA-SC).1 Since the first synthetic preparation of zeolites by
Barrer in the 1940s, zeolites have been widely used as catalysts
and catalyst supports in petroleum and chemical industries,2−4
as ion exchangers in detergents, and as sorbents in separation
processes. Today, they constitute more than 40% of all solid
catalysts used for oil refining, petrochemical processing, and
fine chemicals.5
The remarkable properties of zeolites in these catalytic and
separation processes are closely related to their well-defined
microporous structure.6,7 Notably, the intracrystalline molec-
ular mobility in the zeolites is the determining factor of the
overall reaction rate and separation efficiency. However, the
intrinsic micropores (typically <2 nm) usually impose severe
constraints for mass transfer of reactants/products to and away
from the active center, especially when bulky molecules are
involved. Diffusion, as the main mechanism of mass transfer, is
a crucial factor in deciding the catalytic properties (activity,
selectivity, and lifetime) and the utilization efficiency of the
zeolites in many reactions and separation processes.8 More-
over, the slow transport in zeolite microporous channels could
lead to side reactions, significant coking, rapid deactivation of
catalysts, and most importantly the waste of zeolite materials
and energy. One fundamental approach to minimize the
diffusion limitation is to shorten the diffusion path length,
which can be realized by developing hierarchically porous
materials that integrate porosities of multiple levels in a single
solid body. Therefore, hierarchically porous zeolites are
regarded as the most promising catalytic materials for
industrial applications.9
Many classes of organisms among both plants and animals
contain hierarchical networks of interconnected pores to
maximize the mass transport and increase the rates of reactions
for optimal efficiency and least energy consumption (Figure
1).10,11 Water transport in leaf vein systems is an essential part
of plant growth and development. The efficient water transport
via the leaves is mainly achieved by a two-level hierarchy
consisting of the main veins and smaller capillaries. Our
respiratory system is a highly efficient natural construction
enabling both fast mass transport with minimum resistance and
effective O2−CO2 exchange between air and blood. The lung
also contains a hierarchically porous system with the primary
broad single channel trachea and the secondary large number
of pulmonary alveoli with huge surface area. The blood circuit
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is a closed hierarchically organized vascular system wherein the
pathway of blood starts from a certain point and eventually
returns back to the same point. It is a highly efficient
physiological process promoted by hierarchical distribution
and hierarchical recollection. Theoretical calculations also
confirmed that different hierarchical features of the flow
distribution directly influence the average reaction rates in a
structured catalytic microfluidic reactor.12 Recently, a pioneer-
ing series of bioinspired materials emulating the natural
vascular structure, in which pore sizes decrease along different
scales and end in units of constant size, as in plant stems, leaf
veins, vascular, and respiratory systems, have been fabricated.10
Such biomimics provide hierarchical branching and facilitate
mass transport in both liquid (or gas)−solid and electro-
chemical processes. This is the first macro-meso-microporous
material quantitatively designed and synthesized with optimum
diameter ratios among multiscale pores. It is thus highly
desirable to construct such hierarchical networks of inter-
connected pores within zeolite crystals.10 Importantly, the
synthesized hierarchically porous zeolites should retain a high
zeolitic character; i.e., the additional porosities are introduced
without impairing the intrinsic zeolite micropores. For the
construction of hierarchically porous zeolite structures, Perez-
Ramirez et al.13 proposed increasing the mesopore surface area
without severely sacrificing the intrinsic micropore volume of
zeolite to maximize the hierarchy factor.14
During the past decade, many different strategies to
synthesize hierarchically porous zeolites with both an abundant
secondary porosity and full interconnected mesopores or
macropores have been developed. The preparation methods
can be divided principally into the post-treatment synthetic
routes and the in situ synthetic routes.15,16 The post-treatment,
including the selective desilication/dealumination processes, is
mainly a destructive procedure by sacrificing part of the zeolite
crystals to create larger meso- or macropores.17,18 It usually
results in a loss of crystallinity, and the secondary porosity
generated is often uncontrollable. To solve this problem,
different synthetic approaches, including reaction conditions
and reactants, are adopted. The in situ synthesis approach
usually uses the organic or inorganic templates in the zeolite
crystallization process. It produces hierarchically porous
zeolites with identical or similar components as conventional
microporous zeolites. The key point is to maximize the
interactions between the templates and the zeolite precursors
and thus minimize their phase segregation during the zeolite
crystallization process. It is the determining factor that
influences not only the purity and the morphology of the
zeolites but also the location and the interconnectivity between
the intrinsic micropores and the introduced meso- or
macropores.
Hierarchically porous zeolites combining the intrinsic
micropores with an auxiliary meso- and/or macropore network
of inter- or intracrystalline structure, exhibiting an unimpeded
transport path (macropores) and enhanced micropore
accessibility (mesopores) without sacrificing their intrinsic
catalytic activity (micropores), show great potential in a wide
range of catalytic reactions, such as alkylation, acylation,
rearrangement, Fischer−Tropsch synthesis, hydroconversion,
oxidation, methanol conversions, cracking, and biomass
conversion.19,20 In addition to the above-mentioned excellent
catalytic properties, hierarchically porous zeolites also show
exceptional sorption characteristics useful for the environ-
mental benefits (wastewater treatment, adsorptive desulfuriza-
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Figure 1. Examples for natural hierarchical transport systems. (A) Roots of a tree. Used with permission. Copyright Juimg.com. (B) Leaves. (C)
Blood circuit. Used with permission. Copyright Tooopen.com. (D) Lungs. Used with permission. Copyright Sogo.com.
tion, CO2 capture, and removal of volatile organic compounds)
together with carrier qualities that enable them to be desirable
hosts in biological applications.
In this Review, we will focus on the synthesis and evaluation
of the hierarchically porous zeolites. After this brief
introduction (section 1), in section 2, the recent progress in
the preparation methods of hierarchically porous zeolites is
described. Section 3 outlines the concrete preparations of
different defined types of hierarchically porous zeolites with an
ordered or disordered structure, including micropores and
mesopores (micro-mesoporous zeolites); micropores and
macropores (micro-macroporous zeolites); or micropores,
mesopores, and macropores (micro-meso-macroporous zeo-
lites). The catalytic, environmental, and biological applications
of hierarchically porous zeolites are reviewed in section 4. The
last section (section 5) includes concluding remarks and future
trends. This Review provides a comprehensive overview of
synthesis methods, structural features, and applications of
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hierarchically porous zeolites. The detailed summary, analysis,
and discussion in this Review will enable new researchers in
this field to be more fully familiar with the subject and orient
them to choose the research subdomain they are interested in.
In addition, this Review will help researchers in this field to
understand the latest research progress on the hierarchically
porous zeolites from synthesis to applications.
2. SYNTHESIS
Hierarchically porous zeolites are characterized by the intrinsic
microporosity from the zeolitic framework and the introduced
inter- or intracrystalline meso- or macropore system. Depend-
ing on the introduced pores, the resulting hierarchically porous
zeolites can be further distinguished into (i) hierarchically
micro-mesoporous structured zeolites, (ii) hierarchically
micro-macroporous structured zeolites, and (iii) hierarchically
micro-meso-macroporous structured zeolites. Numerous stud-
ies are carried out to synthesize hierarchical zeolites with the
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advanced pore structure of multiple levels to overcome the
diffusion restrictions derived from sole micropores. The large
variety of synthetic strategies for the construction of pore
hierarchy can be divided into “in situ” and “postsynthetic”
approaches. The in situ approach creates hierarchical zeolites
by fabricating microporous and mesoporous products with or
without the employment of secondary hard or soft templates
during zeolite synthesis. On the other hand, the postsynthetic
approach concerns the post-treatment of the as-synthesized
zeolites to introduce a hierarchical structure into zeolites. In
the following section, these two preparation approaches will be
discussed in detail. Figure 2 gives a general overview of
Figure 2. Overview of the preparation principles and preparation
routes for hierarchically porous zeolites.
different strategies for the introduction of additional porosity.
Besides, the hierarchically porous zeolite materials with
different hierarchical structures obtained by various methods
with concrete examples are summarized in Table 1.
2.1. In Situ Approach
2.1.1. Templating Route. 2.1.1.1. Direct Templating
Route. The synthesis of hierarchically porous zeolites generally
requires mesopore and/or macropore templates (also called
porogens) for the generation of additional porosity and a
structure-directing agent (SDA) for the formation of the
microporous zeolite structure. The mesopore and/or macro-
pore templates are firstly imbedded within the zeolite
precursor slurry and then removed after the zeolite formation
to free additional porosity. Depending on the rigidity (solid or
liquid) of mesopore and/or macropore templates, these
synthesis strategies can be classified into the hard templating
route16,21−147 and the soft templating route.75,148−197
2.1.1.1.1. Hard Templating Route. The hard templating
route involves the use of either nonporous or porous solid
materials with a relatively rigid structure usually used as
sacrificial templates to create the additional porosity during
zeolite crystallization. It can be applied for the synthesis of
hierarchically porous zeolites of a wide range of zeolite
structures since the solid template is chemically inert without
an impact on the zeolite intrinsic structure formation.
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Generally, the synthesis procedure consists of the addition of
solid templates into the zeolite synthetic mixture, the in situ
crystallization of zeolites with the solid templates, and the
subsequent template removal by either calcination or leaching.
The solid templates can be incorporated into the zeolite
crystals during dry-gel conversions198 or zeolite crystalliza-
tion.21 The hard templating route produces zeolites with high
crystallinity, uniform additional porosity, and a tailorable
porous structure. The hard templating route is very suitable to
fabricate hierarchical titanosilicate zeolites due to the special
nature of the titanium species under either acid or alkali
leaching treatments.199,200 Carbonaceous materials,16,21−83
polymers/aerogel/resin,84−109 inorganic solid materials,110−130
and biological material131−147 have been applied as hard
templates to fabricate hierarchically porous zeolites.
2.1.1.1.1.1. Carbonaceous Materials. Due to their excellent
characteristics, such as chemical inertness, structural diversity,
tunable surface functionality, morphology variety, cost
effectiveness, and easy removal, carbon materials, such as
carbon nanoparticles,21−31 nanotubes,32−36,382 nanofibers,37
ordered mesoporous carbon CMK-1 and CMK-3,38−44
ordered porous carbons,16,45−51 and polymers,84−109 are widely
used as hard templates. Whether the obtained porous
structures are ordered and interconnected or not depends on
how the templates are structured and how they interact with
the zeolite synthesis gel during the crystallization process. The
hydrophobic nature of the carbon templates usually makes
them hard to be uniformly dispersed in the hydrophilic zeolite
synthesis gel.52 To avoid the phase separation between zeolite
crystals and carbon materials during zeolite crystallization, the
carbons are usually pretreated with mixture of nitric acid and
sulfuric acids to form surface oxygen species with hydrophilic
features.53,54
Carbon Nanoparticles, Nanotubes, and Nanofibers.
Jacobsen et al. applied carbon nanoparticles for the confined
space synthesis of zeolite ZSM-5 nanocrystals.21 To realize the
confined space crystallization, zeolite precursor gels with an
amount equal to or even lower than the total pore volume of
the carbon matrix were introduced into the carbon materials by
the incipient wetness impregnation method. It is difficult to
strictly constrain the zeolite crystallization within the templates
due to the incompatible nature between the hydrophobic
carbon template and the aqueous zeolitic precursor solution.
Some precursor gel would migrate and crystallize out of the
templates. Thus, dry-gel conversion was applied for this kind of
synthesis, in which the zeolite precursors were reduced to a dry
powder before they were converted in a water-vapor-rich
atmosphere. The mobility in the reaction mixture was greatly
reduced. The composites of dry gels were then crystallized.
They found that, by using an excessive amount of mesoporous
carbon nanoparticles, zeolite crystals nucleated strictly in the
mesopores of carbon nanoparticles.22 The final crystalline size
of the zeolites is decided by the inert mesopore system rather
than the gel composition. When excess synthesis gel was used,
the carbon nanoparticles were dispersed into the zeolite
precursor solution and then encapsulated by the growing
zeolite crystals during the crystalline process (Figure 3A,B).23
Contrary to the zeolite nanocrystals prepared in the confined
space of porous carbons, removal of the embedded carbon
matrix led to zeolite single crystals with intracrystalline
mesopores, which are directly related to the size, shape, and
connectivity of the carbon nanoparticles. Thus, it can be
concluded that, in the carbon-templating synthesis, the
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Table 1. Different Methods Used to Prepare Hierarchical Zeolites

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Table 1. continued

Figure 3. Summary of hard templating routes using carbonaceous materials. Top: schematic diagrams of zeolite-carbon materials. Bottom: TEM
images of as-synthesized mesoporous zeolites. (A, B) Zeolite ZSM-5 single crystal prepared by carbon nanoparticles (12 or 18 nm) with
corresponding electron diffraction inset. Adapted with permission from ref 23. Copyright 2000 American Chemical Society. (C, D) Silicalite-1
single crystals prepared carbon nanotubes (12 nm wide). Adapted with permission from ref 32. Copyright 2001 American Chemical Society. (E, F)
ZSM-5 monoliths prepared by carbon aerogel with the photograph of meso-ZSM-5 monolith inset. Adapted with permission from ref 65,
Copyright 2003 American Chemical Society; and ref 383, Copyright 2013 The Royal Society of Chemistry. (G, H) Ordered mesoporous zeolite
Silicalite-1 prepared by CMK-L carbon replicated from KIT-6 silica. Adapted with permission from ref 38. Copyright 2011 Elsevier. (I, J) Three-
dimensionally ordered mesoporous zeolite LTA prepared from ordered mesoporous carbon. Adapted with permission from ref 49. Copyright 2011
American Chemical Society. (K, L) Mesoporous zeolite ZSM-5 prepared by sugar/silica mixture. Adapted with permission from ref 82. Copyright
2007 American Chemical Society.

generation of either nanocrystals or mesoporous single crystals
largely depends on the synthetic condition that influences the
nucleation rates relative to growth rates.25 The high nucleation
rates favored the formation of nanosized zeolites while the high
growth rates favored the formation of mesoporous zeolite
single crystals.25 The wide availability of this approach was
further demonstrated by the following successful synthesis of
hierarchical zeolites with different frameworks and composi-
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tions and zeotypes, such as mesoporous zeolite single crystals
of BEA (Beta),21 MFI (TS-1,26 ZSM-527), MEL (ZSM-11, TS-
2, and Silicalite-2),28 and MTW (ZSM-12)29 framework
structures, and hierarchical aluminum phosphates AFI
(AlPO-5)31 and CHA (AlPO-34)31 framework structures.
The obtained mesoporous zeolites showed highly improved
diffusion performances and catalytic properties when com-
pared with the conventional microporous materials. However,
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the cavity-like mesopores templated by the spherical carbon
nanoparticles are not open to the external surface of the zeolite
and are only accessible to the micropores, providing very little
contribution to improve the mass transfer.
The use of carbon nanotubes32−36 and carbon nanofibers37
offers an enhanced control over the size and shape of the
introduced mesopores and leads to the generation of accessible
and utilizable mesopores for improved mass transport. Schmidt
et al. was the first to use multiwall carbon nanotubes (12 nm
diameter and several micrometers in length) to produce zeolite
Silicalite-1 with straight and uniform mesoporous channels
(12−30 nm in width, in accordance with the diameters of the
carbon nanotubes) penetrating the whole zeolite single crystals
(Figure 3C,D).32 Mesoporous zeolite Y and ZSM-5 nano-
crystals can also be synthesized in the confined internal
mesoporous space of the carbon nanotubes with an internal
diameter of 20−30 nm.36 The maximum crystal size is limited
by the internal diameter of the carbon nanotubes, thus
realizing the preparation of hierarchical zeolite nanocrystals
with a desirable and controllable size distribution. Similar
mesoporous zeolites were also obtained by using cost-effective
carbon nanofibers as templates.37 The produced mesopores in
zeolite crystals are cylindrical and exhibit low tortuosity.
Chou et al. used carbon nanoparticles in both the
hydrothermal synthesis process and the dry-gel conversion
process for introducing mesoporosity into zeolite crystals.55,56
During the hydrothermal synthesis, the carbon nanoparticles
are excluded from the zeolite crystals, resulting in microporous
zeolites similar to the one synthesized without templates. In
the dry-gel conversion process, the zeolite growth rate is much
slower due to the extremely slow transfer in the synthesis dry
gel caused by the water limitation, thus resulting in a tight
connection between the synthesis gel and the carbon template
and producing hierarchically porous zeolite ZSM-5 with
abundant mesopores. In certain zeolite synthesis systems, the
carbon templates are more effective in dry-gel conversion than
in hydrothermal synthesis.57
Recent developments in the synthesis of carbon-templated
hierarchical zeolites involve the application of microwave
heating methods and the assistance of the fluoride route.
Carbon-templated mesoporous ZSM-5 zeolites were directly
synthesized from the conventional synthesis gel containing
carbon nanoparticles as the mesopore template under
controlled microwave heating.30 Egeblad et al. synthesized a
number of mesoporous zeolites by combining the carbon-
templating strategy with the fluoride route.31 In the fluoride
media, the synthesis of mesoporous aluminum phosphate
materials, including AlPO-5 and AlPO-34, was also proven
possible.31
The effects of carbon templates on the construction of
hierarchical structures in zeolites have also been investigated
with graphene oxide (GO) and graphene nanosheets, which
exhibit unique structural, mechanical, and electronic properties
due to the one-atom-thick carbon sheets. Hydrophilic GO
sheets facilitated zeolite crystallization leading to the formation
of large polycrystalline zeolite crystals,58 while hydrophobic
graphene sheets served as physical barriers to confine zeolite
crystal growth with the formation of smaller crystals.59 GO was
further used in a solvent-free synthesis to realize the control
over morphology and structure of the resulting zeolites. The
addition of GO led to well-dispersed, faceted Si-ZSM-5
crystals, leading to oriented growth of the Si-ZSM-5 crystals
along the c-axis.60
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Carbon Aerogels. Carbon aerogels (CAs) are a version of
the resorcinol formaldehyde (RF) aerogel that are pyrolyzed in
an inert atmosphere.61−63 Compared to the mentioned
mesoporous CMK-n (n = 1−5) templates, carbon aerogels
(CAs) have larger mesopores and thicker mesoporous walls,
making them more suitable mesopore templates to create
intracrystalline mesopores in the zeolites. CAs usually exhibit a
monolithic morphology with a three-dimensional pore system
formed by the agglomerate structures of uniform spherical
carbon particles.64 Thus, these materials are used as hard
templates for the preparation of hierarchically porous zeolites.
The zeolite synthesis gel is introduced into the mesopores of
CAs, and then, zeolite crystals intergrow within the three-
dimensional pore system of the CA monolith. Consequently,
zeolite monoliths with open mesopores can be obtained upon
the complete removal of the carbon matrix by calcination, thus
paving the way for monolithic self-supported mesoporous
zeolite catalysts. By using a CA with mesopore size of 23 nm
and pore wall thickness of ∼10 nm as a template, ZSM-5 (MFI
structure, Figure 3E,F)65 and Y (FAU structure)66 zeolites
containing uniform and abundant mesopores have been
synthesized. The mesopore-size distributions of these zeolites
are very narrow with maxima located at 11 nm, corresponding
to the wall thickness of the pores in the CAs. Besides, the
predominant porosity in CAs can be easily tuned by varying
the molar ratios of starting materials (resorcinol/form-
aldehyde), thus realizing the control over the mesopore size
in zeolites. For example, the ZSM-5 zeolite produced from a
carbonized resorcinol/formaldehyde ratio of 2:1 had a
mesopore volume of 0.98 cm3 g−1, while a ZSM-5 zeolite
produced from a resorcinol/formaldehyde ratio of 1:1 had a
mesopore volume of 0.34 cm3 g−1.67 The obtained hierarchi-
cally porous N-doped biomass-derived carbonaceous mono-
liths served as a cost-effective hard template to synthesize
hierarchically porous ZSM-5 zeolite single crystals with
intracrystalline mesopores of 12−16 nm in diameter.68
Preformed Carbon Templates. Preformed mesoporous
carbons have been widely applied in the synthesis of
hierarchically porous zeolites. The carbon templates with
ordered mesopores are obtained either by replicating the
ordered mesoporous silicates38−44 or by imprinting of colloidal
silicas16,45−50 to give a hierarchical zeolite with ordered
mesopores.
Replications of Ordered Mesoporous Silicates. Ryoo and
co-workers developed a series of ordered carbon mesoporous
molecular sieves (CMK-n, n = 1−5) possessing high surface
area and excellent thermal/hydrothermal stabilities.69−73 The
ordered CMK-1 (cubic structure)69 and CMK-3 (two-
dimensional hexagonal structure)70,71 materials were prepared
by using the ordered mesoporous silicates MCM-4874,75 or
SBA-1576,77 as templates, respectively.
Previous attempts have been made to synthesize MFI
zeolites by directly using CMK-n (n = 1−5) as a hard template.
Cho et al. investigated the conditions for the synthesis of an
ordered mesoporous MFI zeolite using CMK-n (n = 1−5)
mesoporous carbons as a template through the dry-gel
conversion approach (Figure 3G,H).38 They concluded that
the successful replication of CMK in the dry-gel crystallization
process mainly depended on the pore size, humidity, and
framework rigidity. By carefully controlling the condition of
the dry-gel conversion, Sakthivel et al.39 prepared mesoporous
aluminosilicates (RMM-1 and RMM-3) which precisely
replicated the ordered structure of CMK-1 and CMK-3. The
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RMM-1 and RMM-3 appeared to be composite materials,
constructed by mesoporous zeolites with ZSM-5 zeolite
nanocrystals embedded in the pore walls. These works only
obtained an aggregate of zeolite nanocrystals with a disordered
mesopore structure.
Cho et al.44 reported a modified synthetic procedure by
recrystallization of carbon-filled mesoporous SBA-15. The final
product was SBA-15 with zeolitic fragments in the mesopore
wall. Fang et al.41 further reported the successful synthesis of
an ordered mesoporous aluminosilicate with a completely
crystalline zeolite pore wall structure by recrystallization of
SBA-15 using in situ formed CMK-5 as the hard template. This
in situ formed CMK-5 hard template not only helped to
preserve the original ordered mesoporous structure but also
kinetically controlled the crystallization process to avoid the
formation of large crystals. Wang et al.43 confirmed that the
prior formation of a well-developed carbon structure inside the
mesopores of SBA-15 before the synthesis of Silicalite-1/SBA-
15 composites can improve the stability of the meso-structure
of the template during the zeolite crystallization process.
Imprints of Colloidal Silica Nanoparticles and Colloidal
Silica Crystals. The colloidal crystal templating is a popular
method for designing ordered porous carbons.45 Typically,
both colloidal silica nanoparticles and colloidal silica crystals
can be used as hard templates and mixed with a certain carbon
precursor to prepare a carbon template.16 After the subsequent
carbonization and silica dissolution, carbon templates with
ordered meso- or macroporous replicating the initial colloid
silica nanoparticles were synthesized.46 The application of such
porous carbon as a mesopore template resulted in different
mesoporous zeolite single crystals. Pinnavaia et al. demon-
strated for the first time the nanocasting synthesis of uniform
ZSM-5 zeolite nanocrystals using colloid-imprinted carbons
(CICs) as hard templates.47 By varying the particle size of the
initial silica colloid, CICs with different pore-size distributions
were obtained and used as carbon templates to synthesize
zeolite nanocrystals with a controllable size. Fan et al. further
reported the successful synthesis of size-tunable, uniformly
shaped Silicalite-1 zeolite nanocrystals and ordered−imprinted
mesoporous zeolite single crystals within the three-dimensional
ordered mesoporous (3DOm) carbon templates, which
precisely replicated the ordered colloidal silica crystals
composed of size-tunable silica nanoparticles (10−40 nm),
via steam-assisted crystallization (SAC).48 The 3DOm-imprint
method was also used to prepare monolithic 3DOm zeolites.
Chen et al. introduced a modified hydrothermal synthesis
procedure for the synthesis of hierarchical BEA, LTA, FAU,
and LTL zeolite nanocrystals with highly ordered, tunable
intercrystalline mesopores (Figure 3I,J).49 As a hard template,
3DOm carbon with a pore size of around 10−40 nm was firstly
prepared by a replication process from colloidal crystals made
by size-tunable silica nanoparticles. Though the strategy was
time-consuming and costly, it still had the guiding significance
for the fundamental studies of the relationship between the
hierarchical mesopore structures and the catalytic performance
in the zeolites.49
However, the high cost of these preformed carbon materials
has inhibited further industrial applications of their corre-
sponding templated zeolites.78 A promising alternative to the
above porous carbon materials is natural and green materials
that are cheap, abundant, and renewable. For example,
mesoporous carbon materials derived from sugars such as
sucrose79−82 and glucose83 were also reported. A sucrose−
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ammonia mixture was hydrothermally treated and then
carbonized.79 The resultant porous carbon was impregnated
with zeolite precursors; subsequently the mixture was hydro-
thermally treated to achieve the crystalline zeolite architecture.
Homogeneously sized mesoporous Silicalite-1 single crystals
were finally obtained after the carbon removal. Similarly,
another cheap carbon template was in situ fabricated by the
pyrolysis of sugar-impregnated silica gels.82 These well-mixed
carbon/silica composites were directly used for hydrothermal
synthesis and crystallized into hierarchical ZSM-5/ZSM-11
zeolite nanocrystals (Figure 3K,L).
Polymers. In the past decades, polymers, including polymer
aerogels,84−90 polymer microspheres,91−101 and resins,102−109
have also been utilized to synthesize hierarchical zeolite
monoliths with bimodal, trimodal, or even tetramodal porosity.
Particularly, it is interesting to prepare such hierarchically
porous zeolites integrating the advantages of different pore
structures.384 Generally, they are divided into supported and
self-supported zeolite monoliths. For the supported ones, a
layer of zeolite film is deposited on a rigid porous matrix by
either in situ or ex situ coating processes.223,385−388 However,
these supported zeolite monoliths usually have a low zeolite-to-
support weight ratio and suffer from an easy exfoliation of the
coated zeolite film and a restrained mass transport. Contrarily,
the self-supported zeolite monoliths exhibit superior mass and
heat transfer performances and are generally prepared by
zeolite growth within a macro- or mesoporous matrix. These
sacrificial substrates serve as a shape-directing macroporous
template and can then be easily removed, e.g., by calcination,
leaving a hierarchically porous zeolitic structure. The mostly
widely used polymeric templates are carbon/organic aerogels,
close-packed ordered polymer arrays, and resins.
Polymer Aerogels. Resorcinol−formaldehyde aerogel
(RFA), used as the precursor for carbon aerogel, is
characterized by its foamy structure, low-density, and open-
framework. RFA is the polycondensation product of resorcinol
(1,3-dihydroxybenzene) with formaldehyde. The subsequent
drying of resorcinol−formaldehyde (RF) gels with supercritical
CO2 or supercritical acetone can retain the previous gel
structure. The resultant RFAs are used as templates to fabricate
mesoporous zeolites.84−87 As previously noted, mesoporous
ZSM-5 and Y zeolites with high crystallinity were obtained by
the CA template,65,66 but it was difficult to obtain mesoporous
zeolite A by such a rigid-structure casting method. 88
Alternatively, by using RFAs with more structural flexibility,
mesoporous zeolite A (Linde Type A, LTA structure)88 with a
uniform and interconnected mesoporous structure was
obtained. The resultant mesoporous zeolite A exhibited no
crystalline defects, and the introduced mesopores strictly
replicated the intrinsic pores in RFAs. Furthermore, RFA-
templated mesoporous ZSM-5 zeolites exhibited a smaller pore
volume, a larger pore size, and a wider pore-size distribution
than the ones templated from CA templating.89 It was reported
that both mesopore sizes and mesopore volumes in the final
zeolites are decided by the structures of the templates.90
Therefore, CAs can create larger mesopore volumes in
mesoporous zeolite ZSM-5 than those of RFAs due to their
thicker pore walls and low mesopore volumes. Contrarily, the
RFAs with relatively thicker and nonuniform walls resulted in
mesoporous ZSM-5 zeolites with larger mesopores and a
broader pore-size distribution in the mesoporous ZSM-5.
Recently, a novel polymerization-induced-colloid-aggrega-
tion process was developed for the in situ preparation of
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Figure 4. Schematic representation of the different preparation steps (A−C) of hollow Silicalite-1 spheres (B) and bodies with a regular system of
microcavities (C) and corresponding scanning electron micrographs of (B) hollow Silicalite-1 spheres and (C) Silicate-1 body with spherical
microcavities. Adapted with permission from ref 101. Copyright 2002 American Chemical Society.
uniform hierarchical zeolite microspheres with different
compositions.86,87 Urea and formaldehyde solutions were
added into the nanozeolite colloidal solutions with different
compositions and then in situ polymerized after adding
hydrochloric acid. By simply regulating the polymeric acidity,
the morphology and composition of products were precisely
controlled. The synthesized hierarchical nanozeolite micro-
spheres exhibited a uniform spherical morphology and tunable
secondary pore architecture. The change in morphology of the
samples under different polymerization conditions can be
explained according to the proposed polymerization-velocity
match mechanism.87
Polymer Microspheres. The first three-dimensionally
ordered macroporous zeolites fabricated on the basis of an
assembly of PS microspheres as templates were reported by
Holland et al.91 Such macroporous zeolite monoliths with
varying compositions and varying frameworks can also be
synthesized by the evaporation-induced in situ self-assembly of
PS microspheres and zeolite nanocrystals92 or by casting
different zeolite nanocrystals into the ordered PS arrays via
infiltration.93−95
Hollow zeolite spheres were fabricated by a layer-by-layer
strategy via an alternative deposition of zeolite nanocrystals
and polyelectrolytes of opposite charges onto polystyrene
spheres of positive charges.96 Different hollow zeolites can be
prepared by either changing the type of zeolite nanocrystals or
changing the thickness of the deposited layers.97,98 Such core−
shell building blocks, which were exactly PS microspheres with
a nanozeolites coating, were also used to prepare macroporous
zeolite monoliths.99 However, hollow zeolite microspheres
obtained by the layer-by-layer method usually exhibited weak
mechanical strength. To solve this problem, Valtchev et al.
reported an effective approach to improve the mechanical
strength of the layer-by-layer structured hollow zeolite
sphere.100,101 The surface charge of the polystyrene (PS)
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microspheres can be easily modified by simply depositing
several layers of different polyelectrolytes, leading to enhanced
electrostatic interaction with the building zeolite particles
(Figure 4A). In this case, PS microspheres can act as sacrificial
templates to fabricate hollow zeolites with hierarchically micro-
macroporous structures (Figure 4B). These uniform spherical
templates can further self-assemble into a highly ordered
microporous structure simply by the centrifugation or
sedimentation processes (Figure 4C). Therefore, zeolite
monoliths with a three-dimensionally ordered macroporous
structure are another main product when PS microspheres are
used as macroporogen templates.101
Resins. Using an ion exchange resin as a hard template has
also been reported for the synthesis of mesoporous zeolite
materials. In a typical procedure, the zeolite synthesis gel firstly
was adsorbed onto the anionic ion-exchange resin beads, and
then, the mesoporous Silicalite-1 zeolite microspheres were
obtained after crystallization followed by calcination.102 By this
method, hierarchical palladium-containing zeolite has been
reported.103 However, such ion-exchange resins cannot be
used to synthesize AlPO-n zeolites due to the existence of
positively charged precursor species in the initial AlPO-
synthesis gels.104 Naydenov et al. introduced a modified
method to prepare transition-metal-modified AlPO-5 spheres,
allowing for the introduction of any metal ions into the AlPO-
material. Vanadium-modified mesoporous AlPO-5 spheres
were also prepared.105
Besides, polyurethane foams (PUFs) can also be used as a
hard template. Yoon et al. used PUF to prepare hierarchical
zeolite Silicalite-1 and ZSM-5 monoliths with ramified and
interconnected macropores together with tailorable sizes and
shapes.106,107 It is interesting that this PUF template gradually
decomposed with the growth of the zeolitic shell, and the
decomposed fragments of PUF in turn accelerated the
crystallization rate. In the previous reports, bimodal porosity
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Figure 5. (A) Schematic representation of the crystallization process of macroporous zeolite crystals and corresponding (B) SEM image of the
mesoporous silica spheres (MSPs). (C) TEM image of an individual zeolite crystal with corresponding zone axis electron diffraction pattern inset.
Adapted with permission from ref 120. Copyright 2014 John Wiley & Sons, Inc.
(micro-mesopores, micro-macropores) or even trimodal
porosity was achieved by zeolite crystallization within
appropriate macro- or mesoporous supports. However, for a
self-supported zeolite monolith, it is still a challenge to
simultaneously control the porosity on all length scales. An
ideal hierarchically porous monolithic zeolite should contain
macroporosity for fast mass transport, mesoporosity for precise
shape selectivity, and microporosity for catalytic active sites.
The macropores usually stem from the supports; the
mesoporosity can be either the intercrystalline ones from the
nanozeolite aggregates or the intracrystalline ones.65,108
However, the intercrystalline mesopores are unstable and
collapse during the catalytic process. Li et al. developed a one-
pot synthesis strategy of a ZSM-5 zeolite monolith with
controllable tetramodal porosity by using PUF as a sacrificial
support through a simple steam-assisted crystallization (SAC)
process.109 A concentrated ZSM-5 precursor solution was
soaked into the macropores of PUF supports. After PUF
supports were removed by SAC treatment, the first-modal
macroporosity in the resultant zeolite monolith (pore size of
∼33 μm) was formed from the PUF structure, the second-
modal macroporosity (pore size of 0.2−1.7 μm) from the
aggregated zeolite nanocrystals (crystalline size of ∼500 nm) in
the voids of PUF, the third-modal template-free-derived
mesoporosity (∼53 nm) from the intracrystalline voids in
the zeolite nanocrystals, and the fourth-modal microporosity
from the intrinsic microporosity.
In conclusion, a monolithic zeolite with a porous hierarchy
can be prepared by the zeolite growth onto macro- or
mesoporous resins. However, the simultaneous control over
multipores inside monolithic zeolites is poor. The macropores
templated by the resin are larger than 100 mm, and the
macropores in the resins are not fully utilized. The mesopores
in the hierarchical monolithic zeolite stemming from the
intercrystalline mesopores aggregated by the zeolite nanocryst-
als are unstable and easily collapse during the catalytic process.
Thus, it still remains a great challenge to overcome this
drawback.
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2.1.1.1.1.2. Inorganic Solid Materials. In addition to
carbonaceous materials and polymers, other inorganic solid
materials, such as mesoporous silica spheres110−120 and
calcium carbonate nanoparticles,121,122 were also used as
secondary templates in hierarchical zeolite synthesis.
Mesoporous Silica Spheres. It was reported that the usage
and removal of polymer templates always result in environ-
mental pollution. Besides, the calcination process to remove
the polymer template cores causes considerable shrinkage
(more than 20%) or even fracture in the products.96,99
Alternatively, mesoporous silica spheres can be applied as hard
templates to avoid the critical template removal step since they
serve both as a mesopore/macropore template and as the silica
nutrients for the growth of the zeolites, leading to their
continuous digestion during the zeolite crystallization.
Currently available methods involve the coating of these
mesoporous silica spheres with zeolite seeds through a layer-
by-layer deposition process,110 resulting in hollow capsules
with homogeneous and dense zeolitic shells111 or robust
zeolitic membranes with three-dimensional closed112/inter-
connected113 macroporous structures. To further improve the
mechanical stability and intactness of the hollow structure, a
seed-induced hydrothermal crystallization process was devel-
oped to fabricate uniform hollow zeolite spheres with much
lower breakage ratio (<2%) and higher mechanical stability
due to the better intergrowth of zeolitic crystals formed under
hydrothermal conditions compared to those prepared from the
vapor phase transport (VPT) method.114 Besides, the
coordination between the zeolite shell intergrowth rate and
the silica core dissolution rate in this approach was reported to
be the key factor for the formation of perfect hollow zeolite
spheres.115 Similarly, Xiong et al. used spherically mesoporous
SBA-15 as a silicon source and substrate to prepare hollow
zeolite ZSM-5 spheres.116
The uniform mesoporous silica (MS) spheres have also been
employed to prepare three-dimensional porous zeolites with
open or closed macropores.112,113,117 A robust three-dimen-
sional hierarchically macroporous zeolite monolith was
obtained after the hydrothermal treatment of the array of
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Chemical Reviews
Figure 6. Overview of hard templating routes using biological materials. Top: SEM images of biological materials. Bottom: electron micrographs of
final mesoporous zeolite products. (A, B) Silicalite-1 with a stomata structure replicated the leaf of Equisetum arvense. Adapted with permission
from ref 136. Copyright 2003 John Wiley & Sons, Inc. (C, D) Silicalite-1 self-supporting zeolite prepared by the Luffa sponge. Adapted with
permission from ref 138. Copyright 2006 Elsevier. (E, F) Silicalite-1 hollow fibers prepared by the cotton thread. Adapted with permission from ref
142. Copyright 2007 Elsevier. (G, H) ZSM-5 zeolite crystals on the carbonized rice husk prepared form the carbonized rice husks. Adapted with
permission from ref 143. Copyright 2005 Elsevier.
nanozeolite coated MS spheres.112,117 However, the closed
macroporous system obtained did not favor mass transport.
Therefore, Wang and Caruso reported a modified procedure to
prepare zeolite monoliths with three-dimensionally intercon-
nected macropores using open mesoporous silica spheres as
templates.113 The resultant zeolitic monolith with an open
three-dimensionally interconnected macroporous structure
demonstrated higher enzyme loadings and activities when
compared with the corresponding zeolite monolith with a
closed macroporous or nonporous structure. Moreover, the
morphologies of these obtained hollow zeolite spheres can be
easily controlled by varying the initial template morpholo-
gies.118 For example, Song et al. reported the synthesis of a
very interesting hexagonal hollow ZSM-5 tube by using
mesoporous silica fibers as both the hard template and silica
nutrient.119
Recently, Machoke et al. developed a simple method to
prepare zeolite crystals with an intracrystalline macropore
system embedded in the zeolitic matrix (Figure 5).120,203 This
approach utilized the steam-assisted crystallization (SAC) of
mesoporous silica particles (MSPs, a in Figure 5A,B) after their
impregnation with tetrapropylammonium hydroxide
(TPAOH). When these impregnated MSPs (b in Figure 5A)
were heated to the crystallization temperature, the outer shell
of the MSPs started to dissolve and increased the silica
concentration on the external surface of these particles, thus
initiating the nucleation and formation of the MFI nanocrystals
on the external surface of the MSPs (c in Figure 5A). The
dissolved silica was consumed in the following crystallization
process to grow and fill the voids between the original packing
of the MSPs (d in Figure 5A). This process continued until
well-shaped crystals were formed. Finally, these MSP cores
were dissolved which left a highly interconnected macropore
network with a porosity of about 45% ± 5% distributed within
the zeolite crystal with a classical MFI morphology (e in Figure
5A,C).120 Macroporous zeolite single crystals ZSM-5201,202 and
TS-1204 have been synthesized with the existing methods and
exhibited a significantly improved catalyst performance.
Calcium Carbonate Nanoparticles. In addition, calcium
carbonate (CaCO3) nanoparticles with spherical morphologies
have also been used to prepare hierarchically porous zeolites.
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Xie et al. reported the synthesis of mesoporous MFI zeolites
using CaCO3 as a hard template, which is cheap and easily
available.121 Interestingly, nanosized CaCO3 (average sizes of
100 nm) could also be added as a solid template into the
solvent-free synthesis system to synthesize hierarchically
porous zeolites by physically mixing, mechanically grinding,
and then heating solid raw materials.122 A potential advantage
of CaCO3 templates is that they can bring some additional
functions into zeolites. For example, the trapped CaCO3 in
zeolite crystals was converted into basic CaO when the
composites were calcined at a high temperature (>600 °C).
The resultant CaO/zeolite products exhibited both strong
acidity from the zeolite and strong basicity from CaO, which
would be very useful for catalysis required for both acidic and
basic sites.11
Other Inorganic Templates. Other inorganic materials have
also been used as templates to construct hierarchically porous
zeolites. A typical example is zeolite Beta, which was used as a
template to synthesize hollow BEA−FAU zeolite composite
spheres through a two-step hydrothermal crystallization
process.123 β-Zeolite was first prepared and used as silicon
sources for the synthesis of Y-zeolite as well as the filler
template for the formation of hollow spheres. Such an
approach successfully avoided the complex removal procedure
of the templates because the macropore template core also
served as the consumption template to serve as the silica
source. The fly ash cenosphere (FAC), an aluminosilicate-rich
waste from power plants, was also employed as the rigid
spherical template and the silica nutrient to prepare hollow
zeolitic microspheres.124 Based on this method, various hollow
zeolite spheres with different frameworks were obtained by
pretreating the FAC with different nanozeolite seeds.124
Furthermore, ice was also used as a template to prepare the
zeolite monolith with a microsized honeycomb structure.125 In
this approach, silica hydrogels were firstly obtained by
unidirectional freezing, in which the rodlike ice crystals acted
as a template for straight macropores.126−129 After removing
the ice crystals by thawing and freeze drying, the silica gel
precursor with a well-ordered channel of 10−50 mm was
obtained. Then, the obtained precursor silica gels were
crystallized under steam at high temperature and pressure by
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Figure 7. Overview of soft templating routes using nonsurfactant polymers. Top: schematic representations of the crystallization processes of
mesoporous zeolite crystals. Bottom: electron micrographs of final mesoporous zeolite products. (A) Conceptional approach to the synthesis of a
zeolite with intracrystalline mesopores using a silylated polymer as the mesoporogen and corresponding TEM images (B and C) of the mesoporous
zeolite: (B) whole-particle specimen and (C) thin-sectioned sample. Adapted with permission from ref 148. Copyright 2006 John Wiley & Sons,
Inc. (D) Schematic illustration of mesoporous zeolites templated from mesoscale cationic polymers and corresponding (E) SEM and (F) HRTEM
images of mesoporous Beta zeolite synthesized. Adapted with permission from ref 151. Copyright 2014 John Wiley & Sons, Inc.

using structure-directing agents (SDAs) to prepare the Silicate-
1 zeolite monolith.
2.1.1.1.1.3. Biological Materials. The hard templating
method is often limited by multistep procedures, which can
be alleviated by using biological templates that are abundant,
inexpensive, environmentally friendly, easily available, and
renewable sources. Biotemplating techniques for the synthesis
of bioinspired zeolites with novel shapes, complex functional
patterns, and hierarchical porosity, in which the natural/
biological tissues and materials are used as templates, could be
of great importance for the development of zeolites with
improved performances.
Biological materials, such as bacteria,145 eggshells,131 spider
silks, 132 insects, 133 sugar cane bagasse, 134 diatoms, 135
leaves,136,137 Luffa sponges,138 wood,139−141 cotton threads,142
rice husks,143,144 starch-derived bread,146 and starch gel,147 are
used as sacrificial templates to create additional pores in
zeolites.
Generally, biomimetic zeolite replicas are achieved by
adsorption or deposition of nanozeolite seeds onto the
biological or natural support surface that was first modified
by a cationic polyelectrolyte.135 This was followed by the
crystal growth process under a hydrothermal139 or chemical
vapor deposition (CVD) treatment.135 For example, Valtchev
et al. reported the very interesting imprinting of zeolite crystals
on a leaf (Equisetum arvense) by a biomineral-silica-induced
crystallization process, in which the intrinsic biogenic silica
source of the leaf support acted as the promoter for the
nucleation of zeolite crystals (Figure 6A,B).136,137 Biomorphic
self-supporting MFI zeolites with hierarchical porosity were
prepared by an in situ seeding and secondary growth route with
a Luffa sponge as the macroscale sacrificial structure
template.138 The zeolitic replica inherited the complex spongy
morphology and the intricate open-porous architecture of
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Luffa (Figure 6C,D). Cotton threads were used to create
hollow structures within zeolites, like bunchy/single hollow
fiber, hollow monolith, or honeycomb structures, due to their
flexibility and facility (Figure 6E,F).142 Furthermore, carbon-
ized rice husk was also used to fabricate ZSM-5 zeolite/porous
carbon composites (Figure 6G,H).143 However, hierarchically
micro-macroporous zeolite monoliths synthesized by using
natural templates usually showed poor mechanical stability and
limited practical applications. Until now, only biomorphic
replicas in the MFI structure (zeolite Silicalite-
1131,135,136,138−142,144−147 and zeolite ZSM-5134,143) and BEA
structure (zeolite Beta137) were synthesized.
2.1.1.1.2. Soft Templating Route. Since the discovery of
highly ordered mesoporous molecular sieves (M41S), soft
templating methods are widely used for the synthesis of
hierarchically porous zeolites.75,389 Soft templates, including
silylated polymers, 148−150 hydrophilic cationic poly-
mers, 151−168 cationic organosilanes, 169−174 and surfac-
tants,75,158−163,165,175−197 exhibit inherent flexibility and
advantages, such as tunable size and adjustable functionality,
and are more versatile than hard templates. During the
crystallization process, these templates not only serve as
physical supports but also directly interact with the silica
species.390−403
Thus, the key factor is to choose the appropriate soft
templates. The soft templates should (1) be stable in alkaline
media even at 140−180 °C as the zeolite synthesis generally
occurs in alkaline conditions, (2) be positively charged to
achieve the strong interaction with negative silica species, (3)
be of suitable mesoscale sizes in aqueous solution, and (4) be
of low cost. Besides, the structure of the soft templates can be
generally and easily controlled either by altering its functional
groups or by changing the packing parameter of the
surfactants. Thus, the soft template route offers a versatile
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Figure 8. (A) SEM images of b-axis-aligned mesoporous ZSM-5 crystals with a chemical structural formula of C-PSt-co-P4VP inset. (B) HRTEM
images of b-axis-aligned mesoporous ZSM-5 crystals with a corresponding electron diffraction inset. Adapted with permission from ref 155.
Copyright 2012 American Chemical Society. (C) SEM images of Beta mesoporous crystals with a chemical structural formula of PDADMA inset.
(D) HRTEM images Beta mesoporous crystals with a corresponding electron diffraction inset. Adapted with permission from ref 156. Copyright
2014 American Chemical Society.

way to tailor the mesopores. Using this method, either inter- or
intracrystalline mesopores can be created in the zeolites by
using designed organic molecules, self-organized molecule
arrays, or emulsion forming agents. There are two general
approaches, one is primary methods in which all the
components (including the surfactant) are introduced into
the synthesis system at the beginning of a one-step synthesis;
the other is secondary methods in which all the components
except the surfactant are introduced at the first step, and the
surfactant is then added at the last step of a two-step procedure
prior to the hydrothermal synthesis.15
2.1.1.1.2.1. Primary Methods. The main characteristic of
the primary methods is one-step synthesis in which all the
components are added at the beginning of synthesis.
Nonsurfactant Polymers. The largest category of soft
templates is macromolecular structures, such as soluble
nonsurfactant polymers. They are largely available and tunable
in their chemical composition, molar mass, and surface charge.
For example, nonsurfactants such as silylated polymers or
cationic polymers proved to be effective primary templates.
The silylated polymers were used as mesopore templates to
create intracrystalline mesopores within the zeolite ma-
trix.148−150 Pinnavaia et al. reported that the −SiO3 units in
the silylated polymer allowed for its graft onto the zeolite
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surface by the formation of covalent Si−O−Si linkages (Figure
7A).148 As the zeolite crystals grew, the incorporated polymers
were phase-segregated from the zeolite matrix, resulting in an
intracrystalline polymer network that was covalently linked to
the zeolite framework. Mesoporous MFI zeolites were
obtained after the removal of the polymer template. Each
particle consisted of randomly oriented small mesopores
(Figure 7B). Besides, the lattice fringes extended throughout
the whole particle, thus indicating that each particle was a
single crystal (Figure 7C). Another successful material was
reported by Wang et al.149 The synthesis was based on
reducing the growth of zeolite crystals. Phenylaminopropyl-
trimethoxy-silane was used as a growth inhibitor to prevent the
further aggregation of the zeolite seeds by silanization. Thus,
the surface functionalization with silane coupling agents of
nanozeolite precursors was considered to be a confined space
synthesis. Furthermore, Hu et al. used organosilanes with
amino-, mercapto-, and allyl- surface groups to control the
growth of ZSM-5 nanocrystals.206 Various organic functional
groups can be regularly grafted on the surface of nanozeolites
in situ, and the resulting nanozeolite particles not only preserve
their nanosize and high crystallinity but also provide a diverse
surface.
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Chemical Reviews
Hydrophilic cationic polymers exhibit a strong interaction
with silica-based species due to their high positive charge and
high alkali resistance stabilities in the high-temperature process
(up to 200 °C). The first example of their use as mesopore
templates was reported by Xiao et al.151−153 They used a
mesoscale hydrophilic cationic polymer (polydiallyldimethy-
lammonium chloride, PDADMAC) to create the intracrystal-
line mesoporosity in zeolite Beta single crystals (Figure 7D).151
The high charge density of the soft templates can effectively
prevent the interfacial incompatibility between the template
and zeolite gel. As mentioned above, the incompatibility always
existed between the uncharged and hydrophobic templates
such as carbons and the negatively charged aluminosilicate
gels. After their self-assembling with aluminosilicate species,
the fiberlike polymers dispersed homogeneously within the
synthetic gel and were then entirely embedded in zeolite
crystals after the hydrothermal crystallization. The calcined
samples had a disordered mesopore system between 5 and 40
nm. These mesopores are partially continuous and opened to
the external surface of the sample, which significantly improved
the accessibility of reactants to the active sites of such
mesoporous H-Beta zeolite (Figure 7E,F). The pore size could
be tuned in a certain range by simply varying amounts of the
soft templates in the synthesis gel during the hydrothermal
synthesis. They further demonstrated a series of nonsurfactant
polymers as dual-function templates for synthesizing hier-
archical zeolites that feature open, interconnected meso-
pores.154 The resultant three-dimensional single-crystalline
zeolite framework was different from previously reported two-
dimensional zeolite nanosheets or agglomerations of zeolite
nanocrystals, in which the surfactant templates create an
ordered mesostructure at the sacrifice of crystallinity. Non-
surfactant polymers have multiple advantages in synthesizing
hierarchical zeolites. They have minimized intermolecular
interactions, which have little influence on the zeolite
crystallization process and thus contribute to the high zeolitic
character of the final products. Besides, the mutual inter-
penetration of the polymers and the zeolite crystalline network
provides disordered but highly interconnected mesopores
within zeolites. Thus, nonsurfactant polymers allow for the
synthesis of mesoporous zeolite single crystals with various
compositions and different framework types. Moreover, extra
functional groups can be added in the polymers to incorporate
desired functionalities into hierarchical zeolites.
Introducing specially oriented and ordered mesopores
within soft templates is still a great challenge. To achieve
this, Xiao and coworkers synthesized a designed cationic
amphiphilic copolymer by treating the copolymer polystyrene-
co-4-polyvinylpyridine with methyl iodide (C-PSt-co-P4VP,
Figure 8A, inset).155 Using this polymer, unidirectional
mesopores of 6−60 nm were introduced within the ZSM-5
single crystals along the b-axis owing to their strong
interactions with the negatively charged silica species (Figure
8A,B). The resulting zeolite ZSM-5 with oriented mesopores
showed a much higher catalytic conversion than that of the
ZSM-5 with nonoriented mesopores in the condensation
reaction of bulky substrates. They further used a conventional
nonsurfactant cationic polymer (polydiallyldimethylammo-
nium chloride, PDADMA, Figure 8C, inset) as a dual-function
template to simultaneously generate micropores and b-oriented
mesopores within zeolite Beta single crystals (Figure 8C,D).156
The quaternary ammonium groups on the polymer served as a
structure-directing agent (SDA) for the zeolite, the same as
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surfactant-based dual-function templates.157−164 It should be
noted that, without hydrophobic segments, PDADMA did not
self-assemble in aqueous solution to form micelles or ordered
liquid crystalline structures that would disrupt the crystal-
lization of the zeolite framework. Besides, the flexible
PDADMA molecules do not affect the crystallization of
zeolites into a thermodynamically stable form, that is, into a
single crystal.
Obviously, the cationic polymer templating approach is not
limited to hierarchically mesoporous ZSM-5 and Beta zeolites,
which were synthesized by mixing mesoscale PDADMAC with
microscale tetraethylammonium hydroxide. By blending
mesoscale cationic polymer templates with other small organic
ammoniums, a series of hierarchically mesoporous zeolites with
various structures are obtained.153 Moreover, the great
diversity of available low-cost industrial cationic polymers
makes it possible to fabricate a wide range of hierarchically
mesoporous zeolites on an industrial scale.
One of the most important problems in the above-
mentioned soft template directed synthesis of hierarchical
zeolite is the long hydrothermal time required for zeolite
synthesis. In particular, it is of notable concern for zeolites with
a relatively high Al content. To solve this problem, a bulk
crystal seeding method was developed and found to be
effective in the hierarchical zeolite synthesis.165 In a typical
synthesis, a purely microporous ZSM-5 zeolite sample with a
Si/Al ratio of 15 was added into the synthesis reaction gel as
the crystallization-accelerating seed. This ZSM-5 zeolite was
composed of aggregates of 100−200 nm bulk crystals. This
resulted in a five-fold rapid generation of MFI nanosheets. It
was reported that seeding is an effective way to minimize the
use of the organotemplate in the syntheses of hierarchically
porous zeolites, resulting in cost and waste reduction and
subsequent economic and environmental benefits.166
Besides the inclusion in zeolite crystals, polymers can also be
used to introduce mesoporosity in zeolites by assisting in the
aggregation of zeolite particles, leading to the formation of
interparticle mesoporosity. For example, Song et al. reported a
novel synthesis route for the self-assembly of Beta zeolite
nanocrystals with the help of mesoscale cationic polymer
PDADMAC, conducting to the formation of bulky Beta
particles containing interparticle mesoporosity.167 Notably, the
mesopores in the bulky Beta zeolite sample are disordered,
which may be due to the use of irregular cationic polymers.151
In comparison, the use of surfactant micelles will usually result
in the formation of ordered mesostructures.75,76 If PDADMAC
was substituted by conventional surfactant molecules such as
cetyltrimethylammonium bromide (CTAB), the bulky particles
were not obtained. This suggested that the mesoscale cationic
polymers with high charge density are easily assembled with
Beta zeolite nanocrystals via their surface hydroxyl groups,
leading to the aggregation of Beta zeolite nanocrystals to form
bulky Beta zeolite particles. It is difficult for the conventional
surfactants with relatively low charge density and small sizes to
create a strong interaction with the surface hydroxyl groups of
Beta zeolite nanocrystals and thus direct the self-assembly of
zeolite nanocrystals. Moreover, polymers can also act indirectly
as flocculating agents. Nanozeolite aggregates with tunable
interparticle mesopores were synthesized by the flocculating
action of a cationic polymer polydiallyldimethylammonium
chloride (PDDA).168 With PDDA, highly-concentrated zeolite
Beta precursor firstly crystallized into zeolite nanocrystals, and
then, these crystals aggregated in a one-step procedure with
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Figure 9. (A) Schematic representation of the crystallization process of mesoporous zeolite using organosilane surfactant as a mesopore structure-
directing agent. Adapted with permission from ref 404, Copyright 2013 Elsevier; and ref 170, Copyright 2006 Macmillan Publishers Ltd. (B) SEM
image and (C) TEM image of mesoporous MFI zeolites. Inset: HTEM image and corresponding electron diffraction. (D, E) Mesoporous MFI
zeolites with tunable mesopore diameters: (D) N2 adsorption−desorption isotherms for mesoporous MFI zeolites and (E) the corresponding pore-
size distribution. Samples 1−3 were hydrothermally crystallized for 5 days at 130 °C, using organosilanes with different chain lengths
([(CH3O)3SiC3H6N(CH3)2CnH2n+1]Cl, n = 12, 16, and 18 for samples 1, 2, and 3, respectively). Sample 4 was crystallized for 2 days at 170 °C
with n = 16. Adapted with permission from ref 169. Copyright 2006 Macmillan Publishers Ltd.

nearly 100% yield, exhibiting interparticle mesopores with very
high mesopore volumes and surface areas. In addition, the
interstitial mesopore size in the zeolite nanocrystals can be
tuned between 40 and 400 nm by varying the polymer
concentration, which is an important parameter.
Organosilanes. In order to create mesopores less than 10
nm in zeolites, Pinnavaia and coworkers used silylated
polymers to effectively construct zeolite morphologies.148
The phase separation between the zeolite precursor and the
organosilanes is minimized due to the formation of the
covalent Si−O−Si linkage. Both the incorporated silicane
fraction and the micropore template were removed after
calcination. For example, polyethylenimine or poly(propylene
oxide) diamine was silylated with glycidoxypropyl trimethox-
ysilane and was then incorporated into the zeolite precursor
gel. The resultant zeolites exhibited intracrystalline mesopores
of 2−3 nm, and the pore size was decided by the silylated
polymers. For these silylated templates, the silylated ends are
anchored in the zeolites while the alkyl fragments created the
mesopores. Tunable length and composition of the alkyl
fraction lead to various hierarchically porous zeolites. A great
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variety of alkylated siloxanes have been reported. Generally,
these templates are divided into cationic organosilane
surfactants, neutral alkyl amino siloxanes, and alkylated
siloxanes. Cationic organosilane surfactants are directly used
as mesopore templates to synthesize hierarchically porous
zeolites, which will be discussed in this section. Neutral alkyl
amino siloxanes and alkylated siloxanes are always used to
functionalize the zeolitic seeds to further prevent the zeolite
growth.
Cationic organosilanes were first synthesized by Ryoo and
coworkers to prevent the separate formation of zeolite and
ordered mesoporous molecular sieves.169 The cationic organic
molecules balance the negative charge of the zeolite frame-
work, or they fill the space in the voids of zeolite framework,
thus stabilizing the formation of zeolite phases under the
required conditions. The organosilane surfactant has a
hydrolysable methoxysilyl moiety connected to a hydrophilic
quaternary ammonium and a hydrophobic alkyl tail.170 The
template 3-(trimethoxysilyl propyl))hexadecyl dimethylammo-
nium chloride ([(CH 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ]Cl,
TPHAC) was added directly to the conventional MFI
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Figure 10. (A) Proposed route for the synthesis of hierarchically mesoporous zeolite. (B) TEM image of mesoporous Y zeolites with SEM images
inset. (C) Nitrogen adsorption−desorption isotherms and pore distribution curves (inset) of mesoporous Y zeolites. Adapted with permission from
ref 176. Copyright 2010 American Chemical Society.
synthesis gel and then hydrothermally converted to zeolite
phase (Figure 9A).169 In a typical zeolite synthesis condition,
the CH3O−Si bonds in TPHAC firstly hydrolyzed to HO−Si
and then formed Si−O−Si or Si−O−Al covalent bonds with
silica or alumina sources. Thus, the surfactant micelles of
TPHAC were well incorporated within the zeolite product.
This was mainly due to the participation of the silica moiety
present in TPHAC to the zeolite crystal formation with
sodium silicate (or tetraethylorthosilicate, TEOS). Meanwhile,
the quaternary ammonium head groups serve as SDA, and the
hydrophobic alkyl tails assemble into a micelle, creating
uniform mesopores within zeolites (Figure 9B,C). Besides, the
mesopore size can be precisely controlled by simply extending
the hydrophobic tail length of the TPHAC template169 or by
adding higher concentrations of the organosilanes.172 Depend-
ing on the different alkyl chain lengths ranging from C12 to C18
in TPHAC, disordered wormholelike mesopores of about 2−7
nm were created (Figure 9D,E).169 An extension of mesopore
size to 24 nm was observed when the synthesis gel was
enriched with the triblock copolymer EO20PO70EO20 (poly-
(ethylene oxide)−poly(propylene oxide)−poly(ethylene
oxide), P123).172 Xiao and coworkers further extended this
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synthesis strategy to synthesize a series of aluminosilicate
zeolites with other zeolite structures like the LTA structure
(zeolite A),171,172 and other framework compositions like
aluminophosphate zeolites with the CHA structure (zeolite
SSZ-13), FAU structure (zeolite faujasite-X),173 AFI structure
(zeolite AlPO4-5),174 and AEL structure (zeolite AlPO4-11).174
For example, it was generally difficult to introduce mesopores
into zeolite X, the high-aluminum version of FAU (Si/Al ratio
1.0−1.5), using the commonly applied desilication route;
however, using the octadecyl derivative TPOAB
([(C2H5O)3SiC3H6N(CH3)2−C18H37]Br), mesopores were
successfully introduced into zeolite X.173
The organosilane surfactant is also a promising candidate to
control the formation of nanosheets, especially for the zeolites
with a low Si/Al ratio that are difficult to be prepared by using
other types of SDAs.173 The direct synthesis of zeolites with
layered structures via the SDA approach is still in an early stage
of development. Recently, this approach has been employed to
prepare hierarchical zeolite nanosheets with MFI and FAU
topologies.405
Surfactants. Monovalent Surfactants. The specially
designed amphiphilic organosilane surfactants and non-
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surfactant polymers offer precise control over mesoporosity,
but they are difficult to synthesize and very expensive. Thus, it
is still desirable to use conventional cationic surfactants, which
are cheap and readily scalable porogens to introduce
mesopores into zeolites. Due to their excellent mesopore-
generating role in the synthesis of ordered mesoporous
materials, surfactants are considered as a reasonable template
to synthesize hierarchically porous zeolites. Initial attempts of
such approaches were based on the use of mixed templates of
monovalent surfactant molecules, such as cetyltrimethylammo-
nium bromide (CTABr, mesopore template) and small organic
ions, such as tetrapropylammonium (TPA+, micropore
template), to simultaneously generate mesoporous and micro-
porous structures in a single zeolite material.406 However, the
interaction of the zeolite with monofunctional surfactants (e.g.,
CTABr) is not strong enough to compete with the zeolite-
forming SDA (e.g., TPA+ for MFI zeolite).15,178,383,407 In most
cases, only a physical mixture of bulk zeolite and an amorphous
mesoporous material was obtained due to the phase separation
caused by the competition between the two different
templating systems.175
To improve the interaction between the conventional
monovalent cationic surfactants and the negatively charged
silica-based species during zeolite synthesis, cosolvents such as
tert-butyl alcohol (TBA) and1,3,5-trimethylbenzene (TMB)
were introduced into the synthesis system, thus facilitating the
condensation of the zeolites around the surfactant micelles and
resulting in the formation of hierarchically mesoporous zeolites
(Figure 10A). Using this method, hierarchically mesoporous
zeolites, such as Y or sodalite, were synthesized (Figure
10B).176 The addition of cosolvent altered the assembly of the
surfactant micelle and increased the charge density of the
micelle, resulting in an enhanced interaction between the silica
species and the surfactant micelles. The resultant materials
exhibited a high surface area and large pore volume from the
self-assembly of zeolite nanocrystals (Figure 10C).176
Cotemplates, such as nonionic amphiphilic copolymer
F127,408 sulfonic-acid-ended organosilane,409 carboxyl-ended
organosilane,410 and amphiphilic organosilane,179 were added
to assist CTABr in synthesizing hierarchically mesoporous
ZSM-5 without the phase separation between the mesoporous
phase and microporous zeolite phase. For example, Wang et al.
reported the preparation of a hierarchically mesoporous ZSM-
5 on the basis of a dual surfactant system made by mixing an
amphiphilic organosilane (3-[(trimethoxysilyl) propyl] octyl-
dimethylammonium chloride, TPOAC) and an ordinary
surfactant (CTABr).179 The effects of different combinations
(different molar ratios) of these two mesogeneous templates
(TPOAC/CTABr) on the mesoporosity of the highly siliceous
mesoporous ZSM-5 zeolites were also studied. CTABr showed
a more effective retarding effect than TPOAC on the
nucleation and crystallization of the MFI structure. The effect
of hydrothermal conditions on the interactions between
surfactant molecules and silicate species has been made
evident and has been shown to also play a crucial role in the
structural transformations of silica precursors. Chen et al.
found that, in the silicate-CTABr system, the original
hexagonal structure of MCM-41 transformed to lamellar and
then to the microporous MFI framework as the reaction
temperature increased from room temperature to 150 °C and
then to 165°C, respectively.210 Besides, several successful
attempts were reported in which microporous zeolites were
crystallized at room temperature.211−213 Thus, the low-
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temperature crystallization of zeolites in the presence of
surfactant micelles seemed to be a possible approach to
synthesize hierarchically porous zeolites. There were a few
reports on the synthesis of LTA (Linde type A) zeolite
nanocrystals with CTABr.207−209 In these procedures, the
organic surfactant was used as a capping agent to effectively
minimize the crystalline size of the zeolite. The surfactant
prevented further crystal growth by covering nanoparticle
surfaces by electrostatic attraction, coordination bonding, or
hydrogen bonding, or even using weak van der Waals
interaction to the surface atoms.180 The observed hierarchically
porous structure in the products followed a two-stage growth
mechanism. Small zeolite nanoparticles were formed and
assembled around the CTABr micelles at the early stage of the
gel evolution. The slow crystalline rate of the amorphous phase
and the low growth rate of the formed crystals kept the CTABr
micelles within the crystalline domain during the second stage.
After template removal, the resultant zeolites exhibited
abundant mesopores due to the intercrystalline voids among
the aggregated zeolite nanocrystals. However, the surfactant
capping was not effective enough to generalize the synthesis of
hierarchical zeolites with other frameworks. The difficulties in
the synthesis of hierarchically mesoporous zeolites using the
conventional monovalent surfactant as soft templates have
been mainly attributed to the weak binding between these
monovalent surfactant molecules and silicate species which
induces the phase separation.411−413
Multivalent Surfactants. To avoid the severe phase
separation observed in the synthesis using monovalent
surfactants, two-in-one (dual-function) templates have been
developed which are surfactant-based.158−161,177 The synthesis
of hierarchically porous zeolites using multivalent surfactants
has been reported.178−181 These surfactants directed a
periodically ordered mesostructure by the self-assembled
supramolecular micelle while micropores were generated by
individual surfactant head groups.182 Thus, the surfactants
should have a sufficiently strong interaction with the growing
zeolite surface to effectively compete with the zeolite SDA to
allow for successful dual-template synthesis of hierarchical
zeolites.183−185 Wu et al. synthesized a mesoporous CHA
zeolite by using C22H45N+(Me)2C4H8N+(Me)2C4H9 as a
mesopore template in a synthesis mixture containing N,N,N-
trimethyl-adamantanammonium hydroxide for the micropore
formation. The mesopore was generated by the growth
interruption of zeolite crystals. Jo et al. further synthesized
FAU-, MOR-, CHA-, and MFI-type zeolite nanocrystals using
the capping effect of the multivalent cationic surfactants in the
hydrothermal synthesis conditions.180 The nanocrystals
formed due to the stronger and multiple binding effect of
the surfactant molecules on the zeolite surfaces when
compared with monovalent surfactants. The agglomerated
zeolite nanocrystals possessed intercrystalline mesopores.
However, the zeolite morphologies (nanoparticles, nanorods,
and nanosheets) and the intrinsic zeolite structures were still
controlled by the surfactants.
The phase separation could be effectively eliminated in the
synthesis using dual-function templates. However, there are
still two major processes which are neither thermodynamically
nor kinetically compatible: the condensation of aluminosili-
cates that forms the micropores and the assembly of surfactants
that creates mesopores. The mesopores induce great strains
inside zeolite structures. A supramolecular self-assembled
mesoscale structure forms rapidly while the zeolites crystallize
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Figure 11. (A) Schematic representation of MFI nanosheets that regularly assembled into multilamellar mesostructures. (B) SEM and (C) TEM
images of multilamellar MFI zeolite nanosheets. (D) Schematic representation of a random assembly of a unilamellar structure. (E) SEM and (F)
TEM images of unilamellar MFI zeolite nanosheets. Adapted with permission from ref 157. Copyright 2009 Macmillan Publishers Ltd.

Figure 12. (A) Gemini-type polyquaternary ammonium organic surfactants: (a) 18-N3-18, (b) 22-N4-22, (c) N4-phe, (d) N6-diphe, and (e) N8-
triphe from top to bottom, respectively (white spheres, hydrogen; gray spheres, carbon; red spheres, nitrogen). For simplification, counteranions
(i.e., Cl− and Br−) for quaternary ammoniums are omitted. (B) SEM and (C, D) TEM of hexagonally ordered crystalline MMS after surfactant
removal. For a structural comparison, an MFI framework model is given in the bottom of part D. Adapted with permission from ref 162. Copyright
2011 The American Association for the Advancement of Science.

slowly. Therefore, it is quite difficult to simultaneously realize Surfactant-based templates create the ordered mesopores
the long-range order of both micropores and mesopores. within zeolites at the cost of the crystallinity of the zeolite
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Figure 13. (A) Detailed description of the template arrangement for the formation of a single-crystalline lamellar structure with good geometric
matching. (B) Schematic representation of the three classes of porosity in the single-crystalline mesostructured zeolite nanosheets with a lamellar
structure (SCZN) with a 90° rotational intergrowth structure. (C, D) HRTEM images of as-made SCZN. Adapted with permission from ref 195.
Copyright 2014 Macmillan Publishers Ltd.
structure. Consequently, most developed zeolites possessed a
lamellar structure with alternated two-dimensional zeolite
nanosheets. For those two-dimensional zeolites (2D zeolites)
constructed by nanosheets or nanosheet assemblies, the third
dimension is limited to 2−3 nm, that is, a 1−2 unit cell. They
exhibited large intersheet mesopore volume, high external
surface area, open porous structures, and a large number of
exposed acidic or catalytic sites when compared with
conventional three-dimensional zeolites.
Long-chain alkyl-quaternary ammonium molecules are
usually used to synthesize mesoporous silica materials due to
the strong interactions between quaternary ammonium species
with the inorganic frameworks.75,186−189 Choi et al. were the
first to succeed in synthesizing lamellar mesostructured zeolites
with dual-function surfactants (C22H45−N+(CH3)2−C6H12−
N+(CH3)2−C6H13, C22‑6‑6).157 The ammonium head groups
induced the conversion of the amorphous silica precursor to
the microporous crystalline zeolitic framework while the self-
assembled surfactant tails directed the zeolite crystal
morphology into the formation of a lamellar mesostructure.
Based on the synthesis condition, the MFI zeolite nanosheets
could be obtained in the form of multilamellar stacked MFI
nanosheets (Figure 11A−C) or unilamellar MFI nanosheets
(Figure 11D−F). For these multilamellar MFI zeolite nano-
sheets, the samples were arranged in a regular way along b-axis,
resulting in the formation of uniform mesopores between
neighboring nanosheets. However, the ordered mesopores
disappeared after calcination.157 An effective approach to
inhibit the collapse of MFI zeolite layers is to introduce silica
pillars in the interlayer space to maintain the ordered
mesoporous structure of multilamellar MFI zeolite nano-
sheets.158
After the success of the C22‑6‑6 dual-functional surfactant,
Ryoo and co-workers extended the synthesis strategy to various
zeolite structures (MFI, BEA, MRE, and MTW) in the form of
nanosheets or nanosponges165,190,191 by varying the localized
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SDA groups in surfactant molecules160−163,192−194 and
mesoporous structures.
A series of Gemini-type multiammonium surfactants (Figure
12A) were synthesized and used as structure-directing agents
(SDAs) for ordered mesoporous molecular sieves with a
crystalline microporous structure.162,182 For example, a
triquaternary ammonium surfactant C18H37−N+(CH3)2−
C6H12−N+(CH3)2−C6H12−N+(CH3)2−C18H37 (18-N3-18)
generated a hexagonally ordered mesoporous molecular sieve
that possessed crystalline walls (Figure 12B−D).162 The
multicationic fractions in the surfactant generated the micro-
pores. Contrarily, the resultant zeolite Beta nanocrystals
aggregated in a disordered arrangement when the micropore
porogenic part in the surfactants is replaced by a phenyl
group, 162 as reported in the synthesis of disordered
mesoporous molecular sieves like KIT-1.414 Besides, the
average thickness of the framework is directly decided by the
quantities of the ammonium groups in the surfactant. More
ammonium groups led to thicker walls. Moreover, the
mesopore size was tunable from 3.8 to 21 nm by using
1,3,5-trimethylbenzene (1,3,5-TMB) as a micelle-swelling
agent.157
Recently, Xu et al. reported that aromatic groups introduced
into the hydrophobic tail of the surfactant molecules195,196 not
only provide π−π interactions that could stabilize the lamellar
micelle but also adjust their configuration to geometrically
match the MFI zeolitic framework (Figure 13A). It was found
that the dual stabilization effects made by multiple positively
charged ammonium heads and the strong π−π interactions in
the surfactant template energetically favored the formation of
an MFI zeolite framework with a 90° rotational structure
(Figure 13B). The resulting zeolite nanosheets had a
hierarchically micro-meso-macroporous structure, in which
the primary microporosity formed in the MFI nanosheet and
the secondary mesopores in the 90° rotational boundary, and
the tertiary macropores were constructed by the mutual
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Figure 14. (A) Schematic illustration presenting the distributions of the micropore template (TPA+) and the silanization agent (PHAPTMS). (B,
C) TEM images of n-ZSM-5 zeolite nanocrystals silanized by 12% PHAPTMS and precrystallized at 90 °C. Adapted with permission from ref 214.
Copyright 2009 American Chemical Society.
pillaring between the plates. A theoretical analysis further
confirmed that the coexistence of multiple quaternary
ammonium heads and aromatic group tails in one surfactant
molecule would significantly reduce the binding energies for
mesostructured zeolites. Furthermore, they realized the
cylindrical assembly of surfactants by introducing azobenzene
into the hydrophobic tail of a surfactant with a diquaternary
ammonium head group. This allowed the formation of ordered
mesoporous MFI zeolite with an ordered two-dimensional
square mesostructure (Figure 13C).197
2.1.1.1.2.2. Secondary Methods. As previously defined, the
secondary methods contain a two-step synthesis process, in
which all the components except the surfactant are added in
the first step, while in the second step the soft template can
either assist the assembly of zeolite seeds into hierarchically
porous structures149,169,214−218,415 or form microemulsions/
reverse micelles for “confined space synthesis”/“steam-assisted
conversion” of hierarchically porous zeolites.219−222,416
Soft Template-Assisted Assembly of Zeolite Seeds into
Hierarchically Porous Structures. Neutral organosilanes, such
as phenylaminopropyl trimethoxysilane (PHAPTMS), were
also used to introduce mesopores in zeolites. Serrano and
coworkers reported a multiple-step seed-silanization route to
synthesize zeolite nanocrystals with extremely small crystal
sizes and enhanced surface area and mesopore volume by
interrupting the zeolite crystallization process through seed
silanization.149 The method was based on hindering the zeolite
growth by modifying the zeolite seeds with PHAPTMS to
avoid aggregating. The incorporated organosilane groups
created interparticle mesopores among zeolite nanocrystals.
The type and quantity of these organic fractions are key factors
to decide the textural properties of the resultant zeolites. By
this method, aggregates of zeolite (ZSM-5 and Beta)
nanocrystals with interparticle mesopores were obtained.149
The resultant MFI zeolites have identical textural properties
with the ones templated by TPHAC described in the previous
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section as part of the primary method.169 Both methods
resulted in the aggregation of crystalline zeolite nanocrystals
(10 nm) and created a large total surface area of 590 m2 g−1
and a uniform mesopore size centered at about 5 nm. The
study on the effect of the nature of surface-silanization species
on the synthesis of hierarchically porous zeolite ZSM-5
nanocrystals was further carried out and showed that
PHAPTMS was the best choice.415 Moreover, they studied
the effect of the main synthesis variables in order to obtain
Beta zeolite samples with large external surface area and high
pore volume. The mesoporosities of these nanozeolites were
easily controlled either by varying the precrystallization
conditions or by changing the quantity or the type of the
organosilane.216
Based on their previous studies, Serrano et al. synthesized
mesoporous zeolite ZSM-5 by the crystallization of organo-
silane (PHAPTMS)-functionalized zeolite nanoseeds under
hydrothermal conditions. The removal of the structure-
directing agent and organosilane was made by calcination.214
The anchoring of organosilanes on the external surface of the
zeolitic seeds was a decisive factor to prevent the nanozeolite
from further growing into large crystals (Figure 14A). The
resultant mesoporous ZSM-5 zeolite particles of about 300−
400 nm were aggregations of ultrasmall zeolite crystallites
below 10 nm with a significant degree of intergrowth (Figure
14B,C).
Moreover, it was found that, due to the strong interaction
between the silanization agent and the linear alcohols, the
viscosity of the gel decreased, and the silanization degree of the
nanozeolites increased by combining silanization with
alkoxylation by adding alcohols like 2-propanol or meth-
anol.217 For example, based on this strategy, Zhu et al.
synthesized hierarchically mesoporous zeolites through the
direct self-assembly of the kinetic controlled zeolite seeds. The
resultant materials exhibited intercrystalline or intracrystalline
mesoporosity.218 It was realized by a two-step procedure. The
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zeolite synthesis gel was firstly aged at 100°C for various time
intervals to form sub-nanocrystals (zeolite seeds) with various
degrees of polymerization.218 Subsequently, the surfactant was
added to direct the self-assembly of these sub-nano-pre-
crystalline zeolites in hydrothermal synthesis conditions.
Finally, either a mixture of mesoporous silica and microporous
zeolite; mesoporous zeolites with cubic shape; or aggregates of
nanocrystals with intercrystalline mesopores were obtained
depending on the aging time of the zeolite seeds.218
Simple alkylated siloxanes (alkyl = methyl, propyl, and octyl)
were also reported by Srivastava et al. to synthesize
mesoporous ZSM-5.215 The size of zeolite nanocrystals was
reduced to 20 nm by adding alkyltriethoxysilane into the
conventional zeolite synthesis gel. Such an alkyltriethoxysilane-
mediated synthesis method can effectively control the size of
the zeolite crystals, particle morphology, and mesoporosity.
Use of Microemulsions and Reverse Micelles. Another
example of soft templating is the synthesis of hierarchically
porous zeolites in microemulsions which function as nano-
reactors for the zeolite growth.416 They are as effective as the
confined voids in porous carbons.16,45−50 Generally, the main
principle in this approach is the phase-separation process of a
mixture (an organic and an aqueous phase) during the zeolite
formation, resulting in a stable, biphasic emulsion formed by
the zeolite mixture (aqueous phase) and the porogen (organic
solvent).219,220 Thus, cosurfactants are necessary to assist
surfactants to avoid the complete phase-separation in the
microemulsion.221 For example, polyoxyethylene nonylphenyl
ether (nonionic surfactant) and butanol (cosurfactant) were
used as emulsifiers to generate the aqueous droplets, consisting
of TEOS/TPAOH/H2O, in heptane (organic solvent).220 For
each aqueous nanodroplet, zeolite Silicate-1 crystallized
independently during the hydrothermal process. The surfactant
adsorption became obvious as these encapsulated zeolites grew
into a certain size, resulting in the aggregation of spherical
microparticles constructed by zeolite nanocrystals. The
resultant material exhibited intrinsic micropores and additional
inter- or intraparticle meso-macropores. The crystallinity and
size of such agglomerates can be easily modified by altering the
aqueous phase and the concentration of water.220 Similarly,
Lee and Shantz also used microemulsions to synthesize
Silicalite-1 microspheres/platelets aggregated by zeolite nano-
crystals.222
In contrast, Li et al. used a two-step approach.219 The
organic phase (CTAM in ethanol) was emulsified in the
aqueous zeolite synthesis solution. The mixture was aged and
then dried at 60 °C to obtain an amorphous dry gel containing
zeolite precursor, microporous SDA, and CTABr micelles
(mesoporogen). The dry gel was then crystallized in the
“steam-assisted conversion” process and transformed into
hierarchically porous zeolite Silicalite-1 with interconnected
trimodal pores. In such a two-step process, the generation of
additional meso- or macropores is separated from the
formation of crystalline zeolite. Thus, it can also be considered
as a crystallization process in which a porous amorphous
material successfully transformed into a hierarchically porous
zeolite.
2.1.1.2. Indirect Templating Route. Hierarchical zeolite
materials, including zeolite composites and zeolite monoliths,
can also be prepared without direct mesopore or macropore
porogens. In the indirect templating route, hierarchically
porous zeolite is synthesized by partial zeolite crystallization
of a mesoporous material (active composite partner) or by the
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deposition of microporous zeolites onto a mesoporous
skeleton (inert composite partner). It is actually a borderline
between direct templating and nontemplating routes. The
indirect templating method typically produces composites
consisting of supported nanosized zeolite crystals. Generally,
these composite partners are divided into inert sup-
ports223,224,385,386,417−430 and active supports.108,225−243,431−461
The inert supports can only be used as a macroporous
template and cannot be used as the initial nu-
trients.223,224,385,386,417−430 The active supports generally
contain one or two components, such as silica materials,
porous glass, aluminosilicates, and titanosilicates, which might
be able to form the building blocks of the zeolite frame-
work.108,225−243,431−459
2.1.1.2.1. Inert Composite Partner. Zeolite composites have
at least one additional material apart from zeolites. Generally,
the synthesis of hierarchically porous zeolite composites
includes a zeolite-shaping process (spray drying, granulation,
tableting, or extrusion) by using either inorganic (silica,
alumina, silica−alumina, or their mixtures) or organic
(cellulose) binders417,418 and ex situ or in situ zeolite coating
on additional supports which should either be able to generate
intercrystalline porosity or be porous itself, respectively. In
most cases, binders such as SiO2 nanoparticles are added to the
suspensions or slurries in order to obtain the stable zeolite
coatings. Physicochemical interactions occurring between a
zeolite and a binder during the shaping process result in
composites with properties different from their simple
mechanical mixture. However, the addition of binders often
causes a decrease in the performance of zeolites due to the
micropore blocking or the inactivation of active sites.419
To overcome these disadvantages, a number of new
methods to synthesize the hierarchically structured zeolite
composites with meso- and/or macropores without binders
were developed. An alternative way is to deposit zeolite
nanoparticles onto the surface of supports with tailored
macropores. Hierarchically structured catalysts with zeolites
as active components and inert porous materials as supports
have been reported. Various porous materials can be used as
inert supports, such as glass,385 porous α-Al2O3,386,420 alumina
ceramic foam,421 stainless steel,422,423 cordierite honey-
comb,424 and SiC.425−429 Generally, the hierarchical zeolite
composites were obtained by a conventional one-step
hydrothermal crystallization. In a typical process, the supports
were first immersed into a zeolite synthesis solution, and then,
the surface of the macroporous supports was loaded or coated
with the zeolite crystals, leading to the desired inter-
macroporosity. Zampieri et al. deposited MFI (Silicalite-1 or
ZSM-5) zeolite nanocrystals on the ceramic foam supports
through an in situ hydrothermal method, resulting in a novel
zeolite−ceramic composite with the bimodal pore system.223
Similarly, Wang et al. reported the layer-by-layer coating of
zeolite nanocrystals on diatom supports.430 However, in these
hierarchically structured zeolite composites, the zeolite loading
and the zeolite−support bond still need to be improved since
weak acidity and poor mechanical strength will significantly
limit their further applications.224
2.1.1.2.2. Active Composite Partners. 2.1.1.2.2.1. Partial
Crystallization of Active Composite Partners. An effective
method to ameliorate the mechanical strength of the
hierarchically porous zeolitic composites is to use supports
that function both as a macroporous template and as initial
silica and alumina nutrients. The active support can be partially
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Chemical Reviews pubs.acs.org/CR Review

Figure 15. Top: (A) schematic of the synthetic procedure for hierarchically micro-meso-macroporous catalysts constructed from zeolite
nanocrystals by a quasi-solid-state crystallization process. Adapted with permission from ref 237. Copyright 2011 John Wiley & Sons, Inc. Bottom:
(B−G) electron micrographs of final mesoporous zeolite products. (B) SEM images and (C) TEM images of hierarchically micro-meso-
macroporous catalysts constructed from zeolite TS-1 nanocrystals. Adapted with permission from ref 237. Copyright 2011 John Wiley & Sons, Inc.
(D) SEM images and (E) TEM images of hierarchically micro-meso-macroporous catalysts constructed from zeolite ZSM-5 nanocrystals. Adapted
with permission from ref 234. Copyright 2011 John Wiley & Sons, Inc. (F) TEM images of hierarchically micro-meso-macroporous catalysts
constructed from zeolite Beta nanocrystals. Adapted with permission from ref 235. Copyright 2011 John Wiley & Sons, Inc. (G) TEM images of
hierarchically micro-meso-macroporous catalysts constructed from zeolite Zr-Silicalte-1 nanocrystals. Adapted with permission from ref 242.
Copyright 2012 Elsevier.

crystallized during the construction of the micro-macropore
structures, resulting in the successful incorporation of the
active component into the monolith structure. These supports
include hierarchically meso-macroporous silica or aluminosili-
cates,227,230,236,238,431−433 sintered kaolin honeycomb,434,462
diatoms,435 biomorphic rattan-derived cellular Si-SiC ce-
ramics,436,437 pumice granules,438 and porous glass.439−443
Generally, the preparation routes are divided into in situ and ex
situ crystallization of the consolidated supports. Various
methods are available for the synthesis of monolithic
structures, such as extrusion,444 inverse replication,445 hydro-
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thermal treatment,227,433 dry-gel conversion,435 and 3D
printing.446 In all these examples, the supports were partly
crystallized and still worked as macroporous supports.
In Situ Crystallization of the Active Composite Partners.
Hierarchically porous Zeolite composites can be prepared by
partial crystallization of mesoporous molecular sieves such as
MCM-41 in the presence of appropriate microporous
structure-directing agents. The resultant zeolite composites
are exactly zeolite nanocrystals supported on or embedded into
an amorphous mesoporous matrix. The synthetic approach of
partial crystallization of ordered mesoporous silicates was
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Chemical Reviews
firstly reported by Jansen et al.225 After the ion exchange with
tetrapropyl ammonium cations (TPA+), hexagonally ordered
mesoporous silica partially crystallized in glycerol medium to
give the formation of mesoporous materials containing very
small protozeolitic or tectosilicate structures within the
mesopore walls. Huang et al. realized the crystallization of
ZSM-5 nanocrystals within the mesopore walls of MCM-41.226
A hexagonally ordered mesoporous silica MCM-41 was firstly
self-assembled from the initial synthesis gel containing the
mesopore template and conventional zeolite synthesis
components. The resultant support containing microporous
structure direct agent TPA+ was subsequently crystallized, and
ZSM-5 nanocrystals were formed within the disordered
hexagonal mesoporous materials.
Ex Situ Crystallization of the Active Composite Partners.
Hierarchically structured zeolite composites can also be
prepared by first impregnation of mesoporous silicas (SBA-
15)433 or mesoporous cellular foams (MCFs)227 with zeolite
seeds and then hydrothermal treatment. Trong On and
Kaliaguine used larger-pore and thick-walled SBA-15 instead
of smaller-pore MCM-41 as the mesoporous support.228,229
The composites were prepared by impregnating calcined SBA-
15 into TPA−OH with designed chemical composition and
following hydrothermal synthesis. By this method, both SBA-
15/ZSM-5228 and SBA-15/TS-1229 were obtained. Similarly,
another mesoporous composite comprising zeolite ZSM-5 was
also obtained by hydrothermal treatment of the TPAOH-
impregnated aluminosilicate gel.447 A similar procedure using
mesostructured cellular silica foams allowed the synthesis of
mesoporous composites containing zeolites ZSM-5 and Y with
larger mesopores.227 MCM-41 was also reported as meso-
porous supports for the synthesis of zeolite Beta nanocryst-
als.230
2.1.1.2.2.2. Complete Crystallization of Active Composite
Partners. As discussed above, a partial crystallization of active
support yields a zeolite-containing composite material while a
complete transformation of ordered mesoporous materials
results in a purely crystalline zeolite phase. The crystallization
of preformed meso- or microporous supports is an efficient
method to prepare zeolitic monoliths with hierarchical
porosity.
Ideally, a hierarchically porous catalyst should possess both
macropores and mesopores of uniform pore size within the
macropore walls which in turn need to be constructed from
tunable microporous zeolite units. To achieve this, a complete
crystallization of bimodally porous preforms containing
mesopores and macropores has been proven to be an efficient
strategy to fabricate hierarchically macro-meso-microporous
structure in all-zeolite materials. The major challenge is to
preserve the macro-mesoporous hierarchy in the preformed
supports during the zeolitization process. Therefore, a careful
process control or a pore-protected synthesis should be made
to yield high-quality zeolites with three-level porosity.
Attempts were made previously to transform the amorphous
silica skeleton into a crystalline zeolite system through the dry-
gel conversion process. The starting porous hierarchy can be
well preserved through a vapor atmosphere but not in solution.
In this way, zeolite Silicalite-1 with hierarchical porosity can be
produced by transforming the skeleton of porous silica into
Silicalite-1 crystals.231 The micropores were from Silicalite-1,
and the mesopores and macropores were formed within
macroporous silica gel. The same approach was followed to
prepare hierarchically meso-macroporous ZSM-5108,232,233 and
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Beta240 zeolite monoliths, which exhibited a higher catalytic
performance in the cracking of large molecules than conven-
tional microporous materials. Sachse et al. developed a
pseudomorphic route to transform a macro-mesoporous silica
monolith into zeolite composites, while maintaining its
complete crack-free morphology allowing its use as a flow-
through microreactor.233 Based on the similar route, an
amorphous silicoaluminophosphate monolith was crystallized
into a hierarchically macro-meso-microporous zeolite SAPO-
34,236 in which the macropores arose from the interconnected
spheres by aggregated zeolite SAPO-34 nanocrystals, and the
mesopores were constructed by aggregated zeolite SAPO-34
nanocrystals. Besides, a seed-induced layer-by-layer synthesis
method239 or a vapor phase hydrothermal transformation238
was also used to synthesize differently shaped binderless zeolite
monoliths with interconnected macro-micropores. A pore-
protection synthesis was proposed by Tong et al., in which
carbon as a solid template was used to preserve the pore
channels of the starting silica monolith as a whole without any
structure collapse during the zeolitization transformation
process.241
A novel glycerol-assisted quasi-solid-state crystallization
(QSSC) method was developed by Chen et al. to fabricate a
series of highly stable and reusable large zeolite blocks with a
hierarchically interconnected three-level micro-meso-macro-
porous structure.234,235,237,242,243 Meso-macroporous materials
(aluminosilicates, titanosilicates, zirconosilicates, aluminosili-
cophosphates, etc., ...) with amorphous architectures and well-
defined macrochannels and very uniform interconnected
interparticle mesopores were used as precursor materials.448,449
Figure 15A displays the schematic representation of the
synthesis of hierarchically micro-meso-macroporous zeolite
TS-1 as an representative example by this glycerol-assisted
quasi-solid-state crystallization (QSSC) process.237 First, the
starting titanosilicates with amorphous architecture were
synthesized via a spontaneous self-formation procedure on
the basis of the chemistry of metal alkoxides450−459 without
any external templates. A droplet of Ti alkoxides and alkoxyl
silanes with a defined molar ratio was simultaneously added
into aqueous solution. The high-speed hydrolysis and
condensation of two alkoxides lead immediately to the
formation of a large number of titanosilicate nanocolloids
which aggregated together to give a gel structure in the droplet
as found in a sol−gel process. Water and alcohol molecules
quickly released from high-speed hydrolysis and condensation
will generate macrochannels as microporous porogens.
Simultaneously, the self-assembly of nanocolloids of titanosi-
licates gave rise to the formation of well-organized and very
uniform mesoporosity.450−459 These meso-macroporous tita-
nosilicate preforms present thus well-defined macrochannels
and interconnected mesopores. The amorphous hierarchical
titanosilicate preforms after drying were first impregnated with
the TPAOH (SDA) solution, then filled completely with
glycerol liquid, and finally gradually transformed into a
crystalline material with the zeolite TS-1 framework. The
macropore channeled structure was preserved owing to the
presence of glycerol liquid in the macrochannels. Furthermore,
the crystallization rate was largely reduced due to the quasi-
solid-state nature of the amorphous hierarchical titanosilicate
preform. The slow crystallization rate allowed the preservation
of initial hierarchical mesoporosity and well-organized micro-
channel arrays. Consequently, the hierarchical micro-, meso-,
macro-pore systems obtained were homogeneously distributed
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Chemical Reviews pubs.acs.org/CR Review

Figure 16. Overview of nontemplating routes by engineering of intergrowth. Top: schematic representation of the formation of hierarchical
zeolites. Bottom: electron micrographs of final mesoporous zeolite products. (A) Top left: structural representation of tetrabutylphosphonium
hydroxide and tetrabutylammonium hydroxide. Top right: schematic representation of the intergrowth between two structures with two different
levels of symmetry. Bottom: schematic representation of the formation of hierarchical self-pillared pentasil (SPP) zeolite by the intergrowth of MEL
(blue, higher symmetry) and MFI (red, lower symmetry). Adapted with permission from ref 468. Copyright 2014 John Wiley & Sons, Inc. (B)
TEM images of the particles before calcination, showing the morphology and the mesopores formed within the intersecting zeolitic lamellae. (C)
High-resolution TEM image of an SPP lamella viewed across its thin dimension. The inset is the fast Fourier transformation (FFT) from the
lamella, consistent with the [010]-zone axis of zeolite MFI. Adapted with permission from ref 573. Copyright 2012 The American Association for
the Advancement of Science. (D) Top left: structural representation of structure-directing agent: (C3H7)3N+−(CH2)5N+(C3H7)3 (diquat-C5). Top
right: schematic representation of the formation of hierarchically organized MFI zeolite. Adapted with permission from ref 251. Copyright 2014
John Wiley & Sons, Inc. (E) Secondary electron and (F) TEM images of the resultant Silicalite-1 zeolites. The inset in part F is the selective area
electron diffraction (SAED) patterns taken from the circled regions in part F. Adapted with permission from ref 251. Copyright 2014 John Wiley &
Sons, Inc.

throughout the final large zeolite blocks. The hierarchically
micro-meso-macroporous zeolite TS-1 materials presented a
well-organized macroscopic network with uniform straight
channel-shaped macropores, arranged parallel to each other
inherited from titanosilicate preforms (Figure 15B). The
macropore walls were constructed entirely from uniform
zeolite nanocrystals in a size of 150 nm with high crystallinity
(Figure 15C), resulting in uniform interparticle mesopores in
the products. Furthermore, the synthesis of micro-meso-
macroporous materials with a whole zeolitic architecture by
using this novel glycerol-assisted quasi-solid-state crystalliza-
tion (QSSC) process is not limited to the synthesis of only
hierarchically micro-meso-macroporous TS-1 zeolite but has
been extended to the synthesis of micro-meso-macroporous
zeolites with different crystalline frameworks, such as zeolite
ZSM-5 (Figure 15D,E),234 Beta (Figure 15F),235 and Zr-
Silicalite-1 (Figure 15G).242 It is envisioned that this synthetic
process can be further extended to synthesize a large variety of
zeolite and zeotype frameworks such as SAPO, AlPO, Y, and X
with highly organized and interconnected hierarchical micro-
meso-macroporosity.
In conclusion, many templating routes were attempted to
introduce meso- or macropores into zeolites during the past
decades, and they can generally be divided into either “direct
templating” or “indirect templating” routes. Different synthesis
methods result in qualitatively different meso- or macro-
porosity, such as the amount, location (intra- or intercrystal-
line), size distribution, and interconnectivity of the additional
X https://dx.doi.org/10.1021/acs.chemrev.0c00016
pores. In addition, different routes have quite different effects
on the intrinsic microporosity, crystallinity, acid-site strength,
and distribution of the zeolites. Efforts should be made to
achieve the optimal balance between the introduced
mesoporosity and the intrinsic microporosity, thus realizing
the better catalytic performances in zeolites.
2.1.2. Nontemplating Route. Hierarchically porous
zeolites can also be prepared without the employment of
secondary hard or soft templates. Several methods including
engineering of intergrowth,173,244−251 additive-assisted crystal-
lization,173,218,252−262 seed-induced synthesis,263−274,463−465 a
controlled crystallization process,275−289,466,467 and designing
special structure-directing agents290−292 have been reported for
the synthesis of hierarchically porous zeolites in the absence of
organic templates.
2.1.2.1. Engineering of Intergrowth. Hierarchical materials
with interconnected micropores and mesopores have been
prepared by branching of zeolite nanosheets by repetitive
twinning or other intergrowth processes. The method is
applicable to all zeolite structures that can either grow
anisotropically as thin layers or support branching at certain
acute angles. Zhang et al. reported a mesoporogen-free
approach for the synthesis of hierarchically structured zeolite
by a repetitive branching mechanism on the basis of the
correlation between the presence of structural twins and
layerlike crystal growth.249 The morphology modifying agents
were tetrabutylphosphonium and tetrabutylammonium ions,
which induced the formation of small amounts of the twin
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Chemical Reviews
Figure 17. Top: (A) proposed evolution process of single-crystalline and defect-free hierarchical nanozeolites. Bottom: (B) low-magnification Cs-
corrected STEM-ADF image of hierarchical nanozeolites. (C, D) High-magnification Cs-corrected STEM-ADF images of region 1 and 2. Inset:
corresponding ED patterns obtained from the entire particles. Adapted with permission from ref 252. Copyright 2019 American Chemical Society.
structure MEL as the MFI-type nanosheet branching points.
They found that, in an environment that favors the epitaxial
intergrowth of two structures with different levels of symmetry,
the higher-symmetry structure (MEL) acts as a link to connect
the lower-symmetry structures (MFI) to create branching. The
regular and repeated intergrowth of these two zeolite
frameworks induced mesopores into zeolites, and the
mesopore sizes were decided by the frequency of branching
(Figure 16A).250,468 The resultant self-pillared pentasil (SPP)
zeolite consisting of orthogonally connected single-unit-cell
thick MFI nanosheets was obtained from the intergrowth of
two different zeolite frameworks (Figure 16B,C).573 In a
similar strategy, hierarchically structured zeolites were
synthesized by sequential intergrowth during a hydrothermal
synthesis using solely (C3H7)3N+−(CH2)5N+(C3H7)3 (diquat-
C5) (Figure 16D).251 The resultant single-crystalline hier-
archical MFI zeolites had additional mesopores within the
zeolite plates and macropores from the intergrown structure
(Figure 16E,F). The organic structure-directing agent (OSDA)
used in this method for the formation of the microporous
zeolite framework was slightly different from the tetrapropy-
lammonium cation. In particular, these OSDAs favored the
generation of ultrathin plates with perpendicularly rotational
intergrowth, resulting in the formation of the hierarchically
porous structure. The synthesis of hierarchical zeolite formed
by the intergrowth of two zeolite crystal structures has been
explored in other systems, such as FAU/EMT,173 EMT/
FAU,244 ETS-4/ETS-10,245 CAN/SOD,246 MFI,247 and
CHA.248 However, only the SPP morphology has been
pubs.acs.org/CR Review
reported to contain zeolite nanosheets of single-unit-cell
thickness.249
2.1.2.2. Additive-Assisted Crystallization. In most cases,
additives, such as growth inhibitor agents,218,252,256−258
polyanion nucleation promoter,253,259,260 and growth modify-
ing agents,173,254,255,261,262,469,470 were used to control the
crystallization process during the hydrothermal crystallization
to obtain well-developed mesopores in microporous zeolites.
The growth inhibitor agents, such as amino or ethanol, were
reported for the formation of nanozeolite aggregates. Zhang et
al. developed a facile amino-acid-assisted strategy for
constructing hierarchically nanosized ZSM-5 with a single-
crystalline structure, defect-free frameworks, and abundant
interconnected interparticle mesopores (Figure 17A).252 It was
achieved by using L-lysine molecules to control both the
oriented aggregation of protozeolite nanoparticles formed at
low temperature and the intraparticle ripening process at high
temperature.
The role of small L-lysine molecules was studied and is
essential since they not only inhibited the crystal growth but
also facilitated the oriented aggregation of protozeolite
nanoparticles in a noncompact manner. For the L-lysine-
assisted crystallization, small L-lysine molecules play thus two
very important roles. On one hand, a small amount of L-lysine
solely acted as a crystal growth inhibitor to produce nanosized
zeolite single crystals, while for excess L-lysine, L-lysine
molecules induced the aggregation of protozeolitic nano-
particles in an oriented way at low temperature in a
noncompact manner. This is particularly applicable for the
targeted modified synthesis that results in reduced zeolite
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Chemical Reviews pubs.acs.org/CR Review

Figure 18. (A) Schematic illustration of the branching mechanism in hierarchical particles (TPOAC-hierarchical-faujasite = T-H-faujasite). The
black lines inside sheet 1 represented EMT nucleation at the edge of a plane (sheet 1) on its (111) and (111̅) faces. The black lines inside sheet 2.
(B) SEM image of the triangular assembly of T-H-faujasite sheets with 3-fold symmetry. The inset shows the cuboctahedral skeletal arrangement of
sheets in T-H-faujasite. (C) Low-resolution TEM image of a hexagonal sheet dislodged by sonication of T-H-faujasite in ethanol. The inset is the
electron diffraction pattern of a selected area in part C. (D) [323]cubic high-resolution TEM image of a sheet (inset FFT) with the FAU/EMT
domains marked and magnified regions I (FAU) and II (FAU/EMT) superimposed by simulated [323]cubic high-resolution images. Adapted with
permission from ref 254. Copyright 2014 John Wiley & Sons, Inc.

crystalline size. Besides, the high-temperature intraparticle
ripening resulted in the formation of defect-free hierarchical
nanozeolites with abundant interconnected interparticle
mesopores (Figure 17B−D). Ni et al. prepared hierarchical
zeolite 4A microspheres in a simple ethanol−water mixed
solvent system without any templates or structure-directing
agents.256 Adding ethanol into the conventional hydrothermal
synthesis could change the physical properties of the synthesis
system, such as alkalinity and viscosity, which could further
affect the interactions among various species in the mixture
and finally lead to products with a different structure and
morphology. The presence of ethanol could hinder the
overgrowth of zeolites crystals and slow down the crystal-
lization process, which favors the self-assembly of zeolite
nanocrystals and their subsequent deposition on the primarily
formed crystals to build hierarchical spheres.257 Similar
phenomena were observed in the synthesis of hierarchically
mesoporous zeolites by a hydrothermal route using hexadecyl-
trimethylammonium bromide (CTAB) as mesoporo-
gens.218,258
Protocols consisting of multiple reaction steps have been
developed for the synthesis of mesoporous nanozeolite
aggregates starting from highly diluted “clear solutions”.259 A
polyanion nucleation promoter (H2PO4−) was first reported by
Kumar et al.260 The presence of ionic species with greater
polarizing ability enhances the process of crystallization
significantly by accelerating the condensation process.260 By
adding H2PO4−, Fang et al. realized the in situ assembly of MFI
zeolite nanocrystals into a mesoporous aggregate with single-
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crystal-like morphology without a secondary mesopore
template.253
Organic additives, such as 3-(trimethoxysilyl) propyl
octadecyldimethylammonium chloride (TPOAC)254 and low-
cost N-methyl-2-pyrrolidone (NMP),262 are able to direct the
formation of zeolite nanosheets. Figure 18A illustrates the
rotational intergrowth of hierarchical FAU/EMT zeolites.254
The EMT zeolite nucleated close to the edge of sheet 1 on
(111) and (111̅) faces followed by branching to generate sheet
2. Further growth results in the formation of interpenetrated
sheets with a hierarchically open house-of-cards arrangement
(Figure 18B).254 The EMT domains within the sheets were
further confirmed by the electron diffraction pattern (Figure
18C,D). Low-cost N-methyl-2-pyrrolidone (NMP) was also
reported as an additive in the synthesis system to direct a
special hierarchical structure in zeolites.262 The resultant ZSM-
5 sample presented a regular house-of-cards-like morphology,
which consisted of some orthogonal sheets.
Simple inorganic salts like Zn(NO3)2 and Li2CO3 instead of
organic molecules can be used as “morphology modifiers” to
generate FAU-type zeolite nanosheets.173,254 The added Zn2+
ions conducted to the formation of a pronounced layerlike
zeolite morphology with a cuboctahedral layer arrangement
very similar to the layered morphology of NaX obtained from
the synthesis with TPHAC.255 The presence of Li2CO3 also
resulted in the formation of well-defined cuboctahedral
nanosheet assemblies but with particularly pronounced
hexagonal (111) plates in a more skeleton-like arrangement.
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Chemical Reviews
Figure 19. (A) Mechanistic illustration of the hierarchically porous zeolite structure formation. (B) SEM and (C) TEM images of the zeolite 3/
0.2/10/1000−20 °C (2d)−120 °C (1d). The high-resolution TEM image was taken from the marked area of the inset. Simulated zeolite crystal
and orientation are shown on the right. FFT of the high-resolution TEM image is shown in the inset. Adapted with permission from ref.275.
Copyright 2015 American Chemistry Society.
Besides, growth modifying agents were also applied in the
formation of layered zeolite crystals. These agents can be
selectively adsorbed on certain crystal faces and change their
growth rate,261 leading to intercrystalline mesoporosity
(hierarchically porous zeolites) or spanning meso- and/or
macropores between the layers (aggregates of layered crystals).
2.1.2.3. Seed-Induced Synthesis. Seed-induced crystalliza-
tion of zeolites in the absence of organic templates has already
been realized in the synthesis of several important zeolites such
as ZSM-5 (MFI),263−265 TS-1(MFI),471 Beta
(BEA),266−268,472 RUB-13 (RTH),269 ZSM-12
(MTW), 270,271 RUB-50 (LEV), 268,272 and heulandite
(HEU).268 In this synthesis strategy, seed crystals of the target
zeolite are synthesized using the conventional method with an
SDA, and then, a small amount of the as-synthesized zeolite
seeds are added to the organic template-free reactant gel to
form the desired zeolite phase. The added zeolite seed crystals
increase the nucleation and crystallization rate and enhance the
quality of the desired zeolite phase by improving the
crystallization.463−465 Hierarchical SSZ-13 microspheres, with
abundant mesoporous channels, have been successfully
synthesized by adding calcined SSZ-13 zeolite crystals in the
starting gel without organic templates.273 This strategy not
only remarkably reduced the production cost and environ-
mental pollution but also significantly decreased the crystal-
lization time and reduced the zeolite crystal sizes. High
concentrations of zeolite nuclei accelerated the growth and
assembly of nanozeolites into easily filterable, stable aggregates.
Nada et al. reported the synthesis of nanocrystalline ZSM-5
with a high quality and yield by using a small amount of seeds
and a short synthesis time.274 The addition of preprepared
zeolite seeds or seed gels into the zeolite reaction gels can
promote the nucleation of the desired phase and suppress side
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products, resulting in a significant decrease of crystallization
times and the reduction of the SDA concentration. The effect
of seed size, synthesis temperature, synthesis time, pH, amount
of seeds and aging time was systematically investigated.
However, the reproducibility is highly dependent on the
quality of the preformed zeolite seeds or gels.274
2.1.2.4. Controlled Crystallization Process. For the syn-
thesis of hierarchically porous nanozeolite aggregates, the
synthetic environment should favor zeolite nucleation rather
than crystal growth. Typical synthesis strategies are the
conventional hydrothermal treatment and dry-gel conversion
process.
2.1.2.4.1. Conventional Hydrothermal Treatment. The
nontemplate approach requires critical control over both the
zeolite nucleation and growth process. By precisely controlling
the kinetics of zeolite nucleation and growth, hierarchically
core−shell structured MFI zeolite single crystals were obtained
(Figure 19A). The zeolite precursor was first aged at low
temperature (T1) for a period (t1) and then heated at higher
temperature (T2) for another period (t2),275 resulting in
hierarchically structured zeolites with nonporous core and a
hyperbranched shell (Figure 19B,C).275 Aluminum-zoning was
the determinant of the branching epitaxial growth behavior,
leading to the generation of a porous shell. Most of the Al-
related acid sites were exposed on the shell and were greatly
accessible.275 It was reported that Al facilitated the nucleation
and slowed down the growth rate of MFI zeolite during the
hydrothermal synthesis.276 For example, hierarchical ZSM-5
with various morphologies and crystal sizes can be obtained by
changing the synthesis conditions, such as the concentration277
of the precursor solution, or the sequence of preparing
aluminate and silicate mixtures.278 Sodium-rich Na2O−Al2O3−
SiO2−H2O precursor suspensions were also favorable for the
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Figure 20. (A) Formation of hierarchical zeolite Beta from a dense precursor gel. (B) SEM image and (C) TEM image of resultant hierarchical
Beta zeolite nanocrystals. Adapted with permission from ref 289. Copyright 2011 American Chemistry Society.
organotemplate-free synthesis of ultrasmall hexagonal EMT
zeolite nanocrystals (6−15 nm in size) at very low temperature
(30 °C).279
Submicron-sized hierarchically mesoporous ZSM-5 spherical
particles, constructed by a thin intergrown zeolite shell and a
micro-mesoporous core formed by the aggregation of 30−50
nm MFI zeolite nanocrystals, were synthesized by regulating
the nucleation and the growth of zeolites.281 Such a unique
hierarchical structure led to a wide interparticle mesopore-size
distribution (3−15 nm) and created more mesopore volume.
The resultant submicrometer spherical catalysts show signifi-
cant improved mass transport and superior catalytic perform-
ance for the self-etherification of benzyl alcohol. A similar
morphology was also reported for ZSM-5.282 On the contrary,
a mesoporous shell of uniformly arranged ZSM-5 nanocrystals
and a microporous rod with a crystalline ZSM-5 core were
synthesized by controlling silica/alumina ratios using conven-
tional hydrothermal treatment under stirring, without any extra
additives or pre-/post-treatments.283 The key to obtain high
mesoporosity in the crystals was the stirring of a synthesis
mixture containing a relatively high concentration of alumina.
Gaber et al. prepared faujasite sheets with a house-of-card
assembled skeleton from inorganic sodium aluminosilicate sols
simply by utilizing the gel “memory” effect of zeolite sols.284
The memory meant that the hydrogels in zeolite synthesis
were not found to substantially change the distribution of
nuclei in the amorphous matrix, and the final crystal size was
unaffected by the treatment.284 The hierarchical morphology
was optimized by suitable starting and final compositions,
leading to the house-of-card assembly of the faujasite sheet
(HCF) morphology with a narrow mesopore-size distribution.
2.1.2.4.2. Dry-Gel Conversion Process. The concentration
of the zeolite synthesis gels greatly influences the final
morphologies of the product.473−476 The concentrated
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reaction mixtures resulted in the generation of mesoporous
aggregates of Beta zeolite nanocrystals, while the diluted ones
led to isolated zeolite nanocrystals.259 Thus, the dry-gel
conversion process, with a highly concentrated zeolite
precursor for promoting nucleation, was found to be a useful
way to construct a hierarchical structure aggregated by zeolite
nanocrystals. By this method, amorphous mesoporous silica
TUD-1 was successfully transformed into zeolite ZSM-5
nanocrystals.285 Bein et al. reported that mesoporous zeolite
Beta nanocrystals were obtained with nearly 100% yield rapidly
without templates.287 Using mesoporous or colloidal silicas
together with tetraethylammonium hydroxide (TEAOH) via a
dry-gel conversion process resulted in assembled nanozeolites
(20 nm) with intercrystalline mesopores of about 13 nm.
Using this method, the Si/Al ratios in zeolite Beta can be tuned
from 10 to 30. The synthesis parameters in this dry-gel
conversion process should be carefully controlled, such as the
drying temperature of the zeolite synthesis precursor, the
induction period, and the humidity level, to ensure a high
crystallinity and abundant mesoporosity. To simplify this
method, Møller et al. used highly concentrated gels in a
hydrothermal treatment to accelerate the zeolite nucleation
and crystallization (Figure 20).289 Dense zeolite precursor gels,
containing aluminum sulfate as the potential nucleation
promoter, were crystallized in a short time, resulting in highly
mesoporous zeolite Beta aggregates. Besides, the mesopore size
was controllable by tuning the crystalline time. With increased
time, zeolite crystals continuously condensed into larger
domains, thus generating larger intercrystalline mesopores.
Hollow spheres with a 10−20 nm thick shell of Silicalite-1
nanocrystals were prepared by a simple self-aggregation
process of nanocrystals without any templates.286 They first
prepared Silicalite-1 nanocrystals via dry-gel conversion, and
later these nanocrystals produced hollow spheres with a shell
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Figure 21. (A) Synthesis of hierarchical zeolite Beta from a concentrated precursor gel. (B) TEM image of resultant hierarchical Beta zeolite
nanocrystals. Adapted with permission from ref 290. Copyright 2011 American Chemistry Society.
of fused nanocrystals under ultrasound. Although silicalite
hollow spheres can be obtained by this simple aggregation
process of nanocrystals, the organization phenomenon
observed in the sonication of the nanocrystals needs to be
further studied. Bein et al. converted an alkali-containing dense
precursor gel to hierarchical zeolite Beta utilizing the steam-
assisted conversion method.287 The individual and uniform
zeolite Beta nanoparticles were first formed and then
condensed into a mesoporous network, resulting in hierarch-
ical self-sustaining macroscopic zeolite aggregates assembled
from Beta zeolite nanocrystals. The dry-gel conversion method
was also applied to the synthesis of hierarchical Beta
zeolites,287,288 ZSM-5,253 and TS-1467 with similar morphol-
ogies. This dry-gel conversion process provided excellent
mesoporosity, although it was difficult to scale up.
2.1.2.5. Special Structure-Directing Agents. Almost all the
reports reviewed above used a traditional structure-directing
agent (SDA) to direct the zeolitic structure. Uncommon cyclic
diammonium templates, such as 3,10-diazoniabicyclo[10.2.2]
hexadeca-12,14,15-triene-3,3,10,10-tetramethyl-dichloride, can
effectively direct the formation to the BEA zeolite framework
in a highly concentrated Na+ system (Figure 21).290 The
pseudomorphic crystallization of mesoporous gel resulted in
the formation of zeolite BEA nanocrystals containing abundant
intercrystalline mesopores. The mesopores were formed due to
the strong affinity between the positively charged cyclic
diammonium templates and negatively charged silicate species
and the effective structure-directing ability of cyclic diammo-
nium templates toward the zeolite BEA framework. This
synthesis method is further expanded to other cyclic
diammonium compounds that can direct the formation of
BEA, MTW, and MFI zeolite nanocrystals.291 Rigid cyclic
diammonium compounds containing phenyl or biphenyl
bridges can effectively direct zeolite frameworks containing
12-membered pore channels, such as BEA and MTW, while a
cyclic diammonium compound connected with two flexible
hexamethylene linkages formed MFI zeolite with a 10-
membered pore channel. With the cyclic diammonium
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compounds, BEA, MTW, and MFI zeolites were formed
with tunable Si/Al ratios.
Cost-efficient alternative templates with a rigid cyclic
geometry, such as piperidine- or imidazole-based dicationic
ionic liquids, were also reported in the synthesis of aggregates
of zeolite Beta nanocrystals.292 Rajkumar et al. prepared a
variety of geminal dicationic ionic liquids and investigated their
potential in the synthesis of zeolites. In their study, several
piperidine- and imidazole-based geminal dicationic ionic
liquids were prepared. It was concluded that only the chair
conformation rather than the boat conformation in the
piperidine-based reagents is favorable for directing zeolite
Beta nanocrystals. Besides, only if the two imidazoles in
imidazole-based templates generate a certain angle, inter-
particle mesopores can be created in zeolite Beta aggregates.292
Though great achievements have been realized in the
nontemplating route for hierarchically porous zeolites during
the past several decades, there still exist many challenges in the
synthesis process. For example, this approach typically involves
precise control over the crystallization process of zeolite
synthesis protocols. No generalized approach has been
achieved for many available zeolite structures. More efforts
should be made to obtain a detailed insight into this synthesis
route and to make significant technological developments.
As noted above, most of the research to date has focused on
in situ approaches to produce hierarchically porous zeolites.
These methods are worthwhile as they can yield solids with
exceptional features. However, their further practical applica-
tions might be limited for the high cost of appropriate hard or
soft templates. Additionally, the key point for the success of the
“in situ approach” is the optimized interactions between the
templates and the silicate or aluminosilicate species in the
zeolite synthesis gels. Therefore, to efficiently mix the zeolite
gel and the templates, elaborate synthesis steps are required.
Besides, efforts should be made to achieve the optimal balance
between the introduced mesoporosity and the intrinsic
microporosity and the best control of the amount, location,
size distribution, and interconnectivity of the additional pores.
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The template removal by combustion is a crucial step to obtain

high-quality hierarchically porous zeolites, which requires
careful consideration especially for large-scale industrial
production. Therefore, the development of effective syntheses
using low-cost template materials together with efficient and
environmentally friendly synthetic strategies allows for the
wide application of these template-based syntheses of
hierarchically porous zeolites in the industries. As for the
nontemplating method, hierarchically porous zeolites are
produced without a mesopore or macropore template but
instead from specially designed synthesis procedures. Most of
these methods are not applicable for industrial synthesis due to
their high costs and complicated synthesis routes.
2.2. Postsynthesis Approach
In contrast to the synthesis strategies discussed above,
additional porosity can also be created within zeolites by
postsynthesis treatment of zeolite crystals that leads to the
formation of secondary meso-macropores.477−485 Generally,
the postsynthesis treatments of previously formed zeolites
consist of demetalation (extraction of framework atoms) or
delamination, which are realized by steam, 2 93 −31 0
acid, 311,486−494 base, 312−340,495−509 or fluoride treat-
ments341,510−512 or more refined approaches such as
swelling,345−348 exfoliating,342,349 or interlayer pillaring with
amorphous silica.350−352 The postsynthetic treatment is largely
used in industry and the main source for the great success in
the commercialization and application of zeolites in general,
yielding superior properties of catalysts and adsorbents with
high stability, designed composition, and desired acid site
speciation.353
The most important advantage of the postsynthetic Figure 22. Schematic representation of the formation of mesopores in
a steaming dealumination process. Reprinted with permission from ref
approach is its simplicity and low cost while the disadvantages 412. Copyright 2014 John Wiley & Sons, Inc.
of this approach include the requirement of very harsh
conditions leading to environmental pollution, defects in
zeolites, partial collapse of the zeolite structure, and low steaming temperature and time are decisive factors for the
control on the selective and precise extraction. extraction of aluminum and the generation of mesopores.300
2.2.1. Demetalation. Generally, the demetalation route This removed Al neutralizes the lattice charges, stabilizes the
involves the treatment of a conventional, purely microporous skeleton Al atoms, and prevents further dealumination.301
zeolite by selective chemical extraction of one constituent, a Therefore, the amount of the extracted aluminum atoms has a
metallic or semimetallic component, from the pristine zeolite limit in a single steaming cycle.302
framework. The typical conditions required to selectively In addition, the removal of aluminum and the migration of
extract some elements from zeolite crystals are quite harsh. silicon lead to an increased framework Si/Al ratio and the
Thus, the extracting process usually involves the usage of formation of mesopores. However, the overall Si/Al ratio of
strong acids or bases,311−341,486−512 or steam,293−310 in which dealuminated zeolites remains almost unchanged since the
the steaming or acid leaching is for aluminum extraction, and micropores and mesopores within the zeolites are partly
the alkaline or fluoride leaching is for silicon removal.354 covered by the debris from the amorphous part and the
Recently, detitanation was also reported as a means to extraframework aluminum species. Mild acids, like diluted
introduce intracrystalline mesoporosity in titanosilicate materi- nitric acid or organic oxalic acid, can also be used to dissolve
als.355−357 these extraframework species. Such a mild acid leaching
2.2.1.1. Steaming. Steaming treatment is the most widely process will not generate more mesopores. The complete
used dealumination method invented in the mid-1960s.293 In a extraction of the amorphous alumina residues finally creates
typical approach, zeolite crystals are treated in a water vapor intracrystalline mesopores with wide size distributions. For
atmosphere at high temperature (>500 °C). Under such example, Lohse et al. reported a mesoporous structure (pore
conditions, the mobility of aluminum and silicon species is size of 10 nm) in zeolite Y formed by a steam treatment.303
enhanced. The aluminum is finally extracted from the zeolite However, the residues of amorphous aluminosilicate fragments
framework, leaving behind vacancies (hydroxyl nest) or partial within the created mesopores seriously blocked these
amorphization of the framework. Some vacancies can be filled mesopores, which can be further removed with HCl treatment.
by free silicon species from the amorphous part while others After this acid leaching, the mesopore size increased to 20
grow to generate mesopores (Figure 22).294−297 The spherical nm.303
or cylindrical mesopores (pore size of 10−20 nm) created by Besides, the framework dealumination can stabilize the
dealumination are either isolated or connected.298 However, pristine Y zeolites (FAU topology), since their high framework
their pore shapes are always uncontrollable.299 Both the Al content results in an unstable protonic form, providing
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zeolites with a larger mesopore volume and a higher Si/Al
ratio. The repeated steaming and acid leaching to remove the
extraframework species can provide zeolites with a larger
mesopore volume and a higher Si/Al ratio. This treatment has
been largely used for the production of ultrastable zeolite Y
(USY), which is the main component of the fluid cracking
catalysts used in crude oil transformation.304 The deal-
umination of the framework can also increase (hydro)thermal
stability.305 Nevertheless, most mesopores formed by steam
treatment are intracrystalline without good accessibility and
thus do not significantly improve the mass transfer of bulky
molecules.307 Some mechanisms in the steam dealumination
process still remain unexplained,308 almost 50 years after their
discovery.309
The main disadvantage of steaming is that the additional
porosity is generated at the sacrifice of framework Al atoms
and the crystallinity. The relatively severe treatment causes
amorphization of the partial zeolite framework, which
decreases crystallinity and partially blocks the active sites.
Another disadvantage is that the quantity and strength of the
acidic sites are modified by the aluminum removal compared
with the pristine zeolite. Besides, the amount and distribution
of Al atoms in the zeolite framework are decisive of the
quantity, the volume, the distribution, and the interconnectiv-
ity of the secondary mesopores.310 Despite these drawbacks,
the steaming treatment is still largely used to create additional
porosity, adjust Si/Al ratio, and increase (hydro)thermal
stability of zeolites.
2.2.1.2. Chemical Leaching. The chemical leaching as a
largely spread post-treatment resulting in dealumination or
desilication procedures, which correspond to the selective
removal of framework aluminum or silicon atoms, respectively,
from the zeolite structure, is an effective method to generate
secondary intracrystalline mesopores. Based on sacrificing part
of the zeolite frameworks, these leaching processes generate
amorphous regions within the crystalline zeolites, and
mesopores are formed after the extraction of the amorphous
debris. In this section, we present a review of dealumination via
acid leaching and desilication methods for the construction of
hierarchically porous zeolites.
2.2.1.2.1. Acid Leaching. Acid leaching was first introduced
by Barrer and Makki. Mineral acids are used to remove
aluminum from clinoptilolite.486 The acid leaching method can
preferentially extract framework aluminum from a microporous
zeolite to directly create mesopores within the crystals. Defect
sites are formed through hydrolysis and breaking of the Si−O−
Al bonds, thus leading to the formation of Si−O− defects and
leaving extraframework alumina species behind. Mineral or
organic acids with different acid strength such as nitric, sulfuric,
or hydrochloric acids and acetic, oxalic, and tartaric acids were
used at different concentrations. The effectiveness of this
technique depends on the nature of the zeolite and acids used.
For example, purely microporous mordenite, Beta, and ZSM-5
zeolites were partially dealuminated in HCl medium in an
autoclave under microwave irradiation at 373 K for 15 min.
Depending on the crystalline framework structure, Si/Al ratio,
and acid leaching conditions, zeolite Beta was much easier to
dealuminate than zeolite mordenite, while zeolite ZSM-5 was
nearly unaffected.487,488 The nature of the acid is a decisive
factor for the final mesopore structure. For example, zeolite
mordenite leached by oxalic acid had a much higher bulk Si/Al
ratio but fewer mesopores than the one by nitric acid, owing to
the higher pH of the oxalic acid solution and in particular the
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ability of the oxalate ions to coordinate with the aluminum
ions.487 Recently, Sun et al. reported the preparation of
hierarchical SAPO-34 with a butterfly-shaped pore system by
hydrothermal synthesis followed by an acid post-treatment.311
They demonstrated the influence of different acids on the
synergic effect of the multipores and acidic sites. The SAPO-34
treated with nitric acid or oxalic acid exhibits multipores
including micropores, mesopores (40−50 nm), and macro-
pores (62−500 nm). However, hierarchical SAPO-34 cannot
be obtained by treating SAPO-34 with butanedioic acid. It was
also found that acidic treatment could optimize the number of
acidic sites of SAPO-34. The main disadvantage of acid
leaching is the decreased number of acid sites leading to the
increased framework Si/Al ratio and acid strength.489 The
creation of mesopores by acid leaching is always accompanied
by the changes in number and strength of acid sites, making it
complicated to separately study their influences on the catalytic
performance. Besides, for the high-silicon-rich zeolites, the low
amount of aluminum distributed in the entire framework will
hardly be removed to generate a notable mesoporosity, since
too few defect sites can be generated.490−492 For example, it is
difficult to induce the mesoporosity in ZSM-5 zeolites by a
dealumination process, due to the low amount of framework
aluminum that can be extracted. As for the low-silica zeolites
(Si/Al < 2.5), dealumination leads to partial structure
collapse.493,494 Moreover, the introduced mesopores are
isolated, and the selective dealumination process cannot create
an interconnected mesopore system. A pulsed field gradient
(PFG) NMR was applied to study intracrystalline diffusion in a
dealuminated Al-rich Y zeolite and indicated that the
mesoporosity generated by such acid leaching did not enhance
the diffusion of large molecules.306
2.2.1.2.1.1. Alkaline Leaching. Alkaline leaching or
desilication refers to the selective extraction of silicon from
the zeolite framework in alkaline medium.326−331 Contrary to
the difficulty for the acid leaching to extract Al atoms with
zeolites of high Si/Al ratio, the alkaline desilication is a
promising approach suitable for zeolite with high Si/Al ratio to
prepare hierarchically porous zeolites due to its applicability as
a postsynthesis treatment of purely microporous zeolites of
high Si/Al ratios.332 The most extensive investigations
concerned with the influence of treatment parameters on the
mesopore formation have been made for zeolite ZSM-5.333
The Si/Al ratio was effectively expanded from about 10 to 1,
and the mesoporosity was generated in ZSM-5 by
desilication.312−314 Besides, its effectiveness has also been
demonstrated for other zeolite framework structures, including
MTW,315 MOR,316 BEA,317 AST,318 FER,319 MWW,320
IFR,321 STF,322 CHA,323 FAU,324 and TON.325
When an alkaline treatment is applied, silicon atoms are
selectively extracted from the zeolite framework, while
aluminum species accumulate on the external surface, playing
an important role in pore direction.313,495 Other trivalent
heteroatoms in lattice positions, such as Fe3+, Ga3+, and B3+,
were also reported as the pore-directing agent.496 Several
routes were reported to control the desilication process within
the optimal range of Si/Al ratios, such as partial detemplation−
desilication,497 microwave irradiation,498 and the use of
alternative bases499,500 or pore-growth moderators.13 More-
over, by combining alkaline with steam501 or acid495
treatments, the mesopore formation was accompanied by
acidity modification.
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Contrary to the acid leaching to extract Al species, the
mesopores created by desilication are mostly interconnected
and highly accessible from the external surface of zeolites,
resulting in improved performances in diffusion-controlled
reactions.312 Based on the hydrolysis of Si−O−Si and Si−O−
Al bonds in an alkaline environment, the mesopores are first
generated on either the outer surface or the defect areas within
the crystalline structure.327,330,502 The hydroxide anions
(OH−) would react with the silanol groups (defect sites)
within the zeolite framework. The extracted silicate anions are
stabilized by the alkali cation, resulting in voids within the
framework. The Na+ ion is the best silicon atom leaching agent
for its superior capability to stabilize silicate anions.491
The alkaline leaching for enhanced adsorptive capacity and
improved catalytic activity was first reported by Young.334 Mao
et al. further systematically studied the desilication methods.335
They used sodium carbonate as the leaching agent to
selectively extract silicon atoms within the zeolite frameworks.
To realize the control over the desilication process, sodium
hydroxide was added to adjust the pH.336,337 Ogura et al.
reported that the alkali treatment with NaOH created
mesoporosity in zeolites, leading to enhanced diffusion
properties and improved catalytic properties.338,339 Further
works by Groen et al.327,340 reported that the introduced
uniform mesopores have a broad pore-size distribution around
10 nm.340 The external surface increased from 40 to 130 m2
g−1 in the treated samples after the introduction of
mesoporosity, but it was at the cost of microporosity.
Ciziek et al.503 found a possible relationship between the
framework Al within the zeolite and the desilication possibility.
Repulsion between the negative AlO4 tetrahedra and OH− was
found to prevent the hydrolysis of Si−O−Al bonds rather than
the hydrolysis of Si−O−Si bonds, and hence, Al would slow
down the dissolution rate. However, these only concerned
unselective dissolution of zeolites but not the mesopore
formation. Groen et al. systematically studied the role of Al on
the controlled formation of mesoporosity in zeo-
lites.327,332,340,501 A framework Si/Al ratio of 25−50 was
reported to be optimal for the controlled desilication of the
zeolites ZSM-5,327 mordenite,316 and ZSM-12.315 At lower Si/
Al ratios, high Al concentrations (Si/Al < 25) prevented the
silicon dissolution and limited the mesopore formation,
whereas too high silicon zeolites with Si/Al > 50 showed
random and too much Si dissolution, resulting in extensive
mesopore generation and serious crystallinity loss (Figure
23).327 The nonuniform concentration of Al in zeolites would
affect the Si removal within the zeolites. Large zeolite ZSM-5
crystals (5−10 μm), with an Al-rich external surface,504,505
dissolved nonuniformly when treated with alkaline solution.331
Based on these studies, Groen et al. reported the influence of
aluminum gradients and the crystalline size of the zeolites to
control the mesopore formation.328 By the use of the Al
gradients in ZSM-5 crystals, they realized the construction of
hollow structured zeolites with an Al-rich shell.328 Besides, the
stability of framework Al within the zeolite is also decisive to
the created mesoporosity.14 For zeolite Beta, the alkaline
leaching dissolves the framework without keeping the Brønsted
acid sites.317 The poor stability of framework Al within zeolites
SSZ-13 is also problematic for their desilication treatment.323
In addition to mesopore formation, desilication also impacts
the composition and aluminum distribution, which are key
properties intimately related to the catalytic performance.312
Zeolites treated by an alkaline solution usually present a
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Figure 23. Schematic representation of the influence of Al content on
the desilication of MFI zeolites in NaOH solution and the associated
pore-formation mechanism. Adapted with permission from ref 327.
Copyright 2004 American Chemical Society.
decreased bulk Si/Al ratio, micropore volume, and crystallinity
while presenting an increased amount of Lewis acid
sites.314,325,506−509 Understanding the individual effects of the
additional porosity and chemical composition of desilicated
zeolites on their catalytic performance is thus highly relevant
for their optimal design. It was reported that the variation both
in chemical composition and in porosity induced by alkaline
treatment significantly influences the catalytic performance of
desilicated ZSM-5 in the liquid-phase alkylation of toluene
with benzyl alcohol.501 Thus, an optimal alkaline treatment is
beneficial for preservation of the Al environment and the
related acidic properties.327
2.2.1.2.2. Fluoride Leaching. Hydrofluoric acid (HF) is
often used to partially etch or completely dissolve silicon-
containing materials. Valtchev et al. reported the first fluoride
leaching, combining a physical and chemical treatment, for
generating a controlled secondary pore.341 The high-energy238
U ion bombardment was used prior to the fluoride treatment
to form amorphous parts in the zeolites which were then
selectively removed by HF.341 The selective removal is based
on the more rapid etching rates of the amorphous versus the
crystalline regions, leading to the formation of macropores
through the entire crystalline structure. The obtained material
showed higher catalytic activity and stable product selectivity
in the conversion of m-xylene to para- and ortho-isomers.
Figure 24 shows the pristine and the corresponding macro-
porous zeolites. The treated zeolite exhibited both similar
crystallinity and similar Si/Al ratio but a negligible increased
external surface as compared with the pristine zeolites. The
method allows changing both the amount and size of the
introduced pores. Besides, no additional framework species
were found. A study of the dissolution of ZSM-5 in HF with
different concentrations reported that a diluted solution was
Al-selective.510 The selectivity in concentrated HF solution was
greatly reduced due to the large presence of difluoride ions
(HF2−) having higher activity which can unselectively remove
Si and Al atoms from the framework. The resultant hierarchical
ZSM-5 zeolite had similar compositions to the parent ZSM-5.
Lately, similar results were obtained with concentrated NH4F
solution, where the release of NH3 produced HF2−.511
Recently, Qin et al. developed a new method based on etching
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Figure 24. (A) Schematic illustration of chemical equilibria in HF-
NH4F mixed solutions. Reproduced with permission from ref 512.
Copyright 2015 Elsevier. TEM micrographs of (B) a parent ZSM-5
zeolite and (C) its hierarchical derivative, obtained by heavy ion
bombardment followed by fluoride etching. Insets: zeolite micropore
volume accessibility in the initial (inset in A) and hierarchical crystal
(inset in B). Reproduced with permission from ref 341. Copyright
2011 American Chemical Society.
zeolites with NH4F.512 Small amounts of HF2− were in situ
generated by the double hydrolysis of NH4F and then used to
extract framework Si and Al atoms.512 The etching species
were homogeneously distributed inside the crystals. The
dissolution kinetics can be controlled by both the concen-
tration and the temperature of the etching solution.
In contrast to steaming or acid or alkaline leaching, this
nonselective treatment using NH4F solution (removing Al and
Si equally) has important advantages in the preparation of
hierarchical materials with additional porosity. This treatment
can be applied to zeolite with Si/Al ratios close to 1. Another
important advantage is the increased number of Brønsted sites
due to the preferential dissolution of defect zones and/or some
nonzeolitic material present in the parent zeolites. The stress in
these zones and the presence of surface hydroxyls make the
defects more vulnerable for chemical etching.
In conclusion, this novel fluoride leaching route using NH4F
solution to hierarchical zeolites with additional porosity is very
promising. The method is universal and independent of either
the composition or the structure of the parent zeolites.
Moreover, the resulting hierarchical zeolites have a similar
composition to their parents, which is quite different from the
steaming or acid or alkaline leaching routes. Zeolite catalysts
and adsorbents can now be modified more rationally by
postsynthesis treatments.
2.2.2. Delamination. Contrary to the intracrystalline
meso- or macropores created by the demetalation approach,
delamination results in the formation of intercrystalline meso-
or macropores in zeolites. After reducing the individual
crystallite size from the micrometer scale to the nanometer
scale in the third dimension, hierarchically porous zeolites
aggregated by nanolayers are obtained.358 The interactions
between the layers in these hierarchically porous zeolites are
relatively weak (van der Waals interaction, hydrogen bonds,
and electrostatic interaction). After the removal of the
template, precursors in the hierarchically porous zeolites with
a layered structure are usually condensed.359 To solve this
problem, the structures or compositions of these precursor are
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postmodified by swelling,345−348 exfoliating,342,349 or interlayer
pillaring with amorphous silica.350−352
The swelling of lamellar precursors with surfactant
molecules is usually the foundation for other postmodifica-
tions. For example, in a typical delamination process, the 2D
zeolite precursor is first treated in alkaline solutions to expand
the interlayer void assisted with surfactants. The obtained
materials usually exhibit a high degree of intercrystalline
(interlamellar) mesoporosity (Figure 25).345 The initial
Figure 25. Schematic representation of the introduction of
intercrystalline (interlamellar) mesoporosity in the layered zeolite
precursor by the delamination and pillaring of an MCM-22 precursor
(MCM-22(P)) via an intermediate swelling step yielding ITQ-2 and
MCM-36, respectively. Reprinted with permission from refs 11 and
345. Copyright 2016 The Royal Society of Chemistry.
swelling procedure is achieved in a high concentration of
hydroxide (OH−) and surfactant with high temperature, which
could reduce the desilication and structure degradation.346
Tsapatsis et al.360 proposed a milder condition to swell the
lamellar precursor at room temperature to protect the layer
structure. Then, Zones et al. reported a new swelling mixture
containing F− and Cl− ions to swell the lamellar precursor in
nearly neutral conditions, leading to increased active sites when
compared with leaching in highly alkaline solution.361 The
hierarchically porous zeolite with a delaminated structure and
intercrystalline porosity was obtained after the ultrasound
treatment of the swollen precursor [MCM-22(P), PREFER,
and Nu-6(1)] to form 2D-zeolites (ITQ-2, ITQ-6, and ITQ-
18), respectively.342
An alternative pillaring step is applied to introduce or to
retain the preformed porosity in hierarchically porous zeolites
with a layered structure. Typically, pillaring can be achieved by
intercalating surfactant molecules into the interlamellar space
to expand the interlamellar distance.362 This approach includes
the impregnation of the surfactant chains with a soluble
material in the interlamellar space and the following hydro-
lyzation in an aqueous solution. Finally, hierarchically porous
zeolites with stable interlamellar mesopores (expanded
interlayer space) are obtained after calcination.158 The
interlayer pillaring with amorphous silica could maintain the
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large interlayer space, which would disappear upon the
calcination of the swollen precursor.352 Wu et al. developed
a versatile method by the interlayer silylation of the precursors
with specially chosen silanes to obtain the interlayer expand
zeolites (IEZs),343,344 which resulted in hierarchically porous
zeolites with stable interlamellar mesopores and high
crystallinity. An additional stabilization of these zeolite sheets
is made through pillaring, and the mesoporous voids created
by the surfactant tails are retained even after calcination.158
The delamination approach leads to the exposure of a larger
fraction of the highly acidic zeolite surface for adsorption and
catalysis. However, the delamination approach is especially
suitable only for a small range of zeolites. The biggest
challenges of the delamination process are the high surfactant
content and the alkalinity used for swelling leading to partial
dissolution of the zeolite framework.
2.2.3. Recrystallization. The recrystallization approach
involving zeolite dissolution and reassembly was first reported
by Goto et al. in 2002513 and later by Ivanova et al. in 2004.364
The first dissolution step is the partial dissolution of a zeolite
framework and the removal of zeolite fragments, while the
second reassembling process is to make these dissolving
species form a mesoporous phase.
The dissolution degree is decisive for structural and textural
properties of the recrystallized products. Various types of
micro-mesoporous zeolites are obtained by tuning the
corresponding recrystallization degree (Figure 26),514−516
Figure 26. Schematic representation of the recrystallization procedure
that leads to different types of materials. Reprinted with permission
from ref 520. Copyright 2013 Royal Society of Chemistry.
including coated mesoporous or mesostructured zeolite
crystals (RZEO-1) formed by mild recrystallization with
intracrystalline and intercrystalline mesopores;364−372,380,517
micro-mesoporous nanocomposites (RZEO-2) containing
cocrystallized zeolites crystals and ordered mesoporous phases
obtained by deeper recrystallization;364−372,513,518,519 and
mesoporous materials containing small zeolitic units (RZEO-
3) synthesized by full recrystallization.364−378
Surfactants are widely used in the recrystallization process to
introduce additional porosity into zeolites.379 The surfactant-
templated recrystallization processes are divided into two
different methods. The first synthesis is the one-step approach
using surfactant templates with alkaline leaching to synthesize
intracrystalline mesoporous zeolite single crystals. Based on the
use of a dilute NH4OH solution, Garcia-Martinez and co-
workers379−381 first introduced a surfactant-assisted route to
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create mesopores within zeolites. Surfactants, such as CTAB,
can direct well-controlled mesopores within different zeolite
frameworks (Y, mordenite, ZSM-5). For example, zeolite USY
(CBV720 with a Si/Al ratio of 15) was first treated by
steaming and then immersed into a solution of CTAB in 0.37
M NH4OH solution (or 0.09 M tetramethylammonium
hydroxide solution, TMAOH). The surfactants’ removal
results in the generation of uniformly distributed intracrystal-
line mesopores.380
The second approach is the two-step approach consisting of
partial-to-total dissolution of the zeolite in NaOH solution and
the subsequent hydrothermal treatment with surfactants, such
as cetyltrimethylammonium bromide or chloride (CTAB or
CTAC). The introduction of well-controlled mesoporosity
into zeolite crystals is based on a crystal-rearrangement theory
(Figure 27A).380 Only when the Si−O−Si bonds were opened
by a cationic surfactant in base condition and transformed into
negatively charged Si−O− species can the structural reorgan-
ization be realized. This approach allowed the necessary
interactions between the surfactant and the zeolite and avoided
the dissolution of the crystals. Almost full retrieval was
achieved during this mesostructuring process. SEM images
(Figure 27B) indicate that the crystalline morphology
remained almost unchanged. The copresence of both addi-
tional mesopores and high crystallinity within the zeolite edges
is confirmed in the TEM images (Figure 27B). Besides, these
intracrystalline mesopores lead to a significantly high hydro-
thermal stability.380 This method successfully avoided excess
silica loss or crystallinity loss of the zeolites and is applicable to
various Si/Al ratio zeolites from a high Si/Al ratio (USY,
mordenite, ZSM-5) to low Si/Al ratio (NaY and NaA),363 by a
pretreatment approach with a weak organic or inorganic acid.
In conclusion, the recrystallization route contains the
primary desilication/depolymerization process and the secon-
dary reassembling process. The former has been applied to
various zeolite types with high Si/Al ratios while the latter has
few reports. The synthesis can be easily controlled by changing
the alkalinity during the desilication step and various
mesoporosities can be introduced into the materials. However,
mesoporosity is introduced into the zeolites at the expense of
microporosity in the recrystallization route. This calls for
further study of the depolymerization/reassembling approach
for its wider use in zeolites with low Si/Al ratios. Finally, the
range of the organic surfactants for the reassembling step
should be widened in order to enhance the variety of the final
hierarchically porous zeolites.
As noted above, most postsynthetic approaches including
steaming and acid or alkaline leaching have been used to
synthesize hierarchically porous zeolites for decades due to
their simplicity, scalability, and low cost. In these methods,
most of the created mesopores are isolated cavities in the
crystals and thus cannot significantly contribute to accelerating
the mass transport. For example, the desilication has poor
capabilities to tailor the mesoporosity and is seriously
restricted by the relevant Si/Al ratio, leaching temperature,
and leaching time. Dealumination decreases the number of
acid sites with the Al-extraction from the framework.
Accordingly, more efforts should be directed toward the
controlled postsynthetic treatment, thus widening the applic-
ability of this treatment. The postsynthesis of hierarchical
zeolites with high structural stability and the design of such
multimodal porous zeolitic materials with a better under-
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Figure 27. Left: (A) schematic illustration of the formation mechanism of surfactant-templated mesopores in zeolite. (a) Original zeolite Y. (b) Si−
O−Si bond-opening/reconstruction in basic media. (c) Crystal rearrangement to accommodate the surfactant micelles and (d) removal of the
template to generate the introduced mesoporosity. Right: (B) electron images of resultant hierarchically porous zeolites. (a) SEM and (b−f) TEM
images of (c) a single crystal of mesostructured zeolite, (d) an ultramicrotomed mesostructured zeolite crystal, and (e, f) the same area of a
mesostructured zeolite as obtained at two different foci to better visualize the two features of this material. Reprinted with permission from ref 380.
Copyright 2012 Royal Society of Chemistry.

standing of the cooperation between different pore systems still

remain great challenges.

3. HIERARCHICAL STRUCTURE
As discussed in section 2, a wide variety of strategies, such as in
situ and postsyntheses, have been so far developed for
generating additional pores, either inter- or intracrystalline or
even a combination of both. The diffusion of molecules
depending on the size and shape of pores plays a central role in
the performance of zeolites. Figure 28 demonstrates the effect
of pore size on the diffusion of molecules with varying
dimensions. The configurational diffusion of these tightly
fitting molecules into the micropores of zeolites is often the
rate-limiting step of a catalytic reaction, and the molecular
diffusivity is much smaller than that in larger mesopores or
macropores.
For the simplest example of a diffusion limitation imposed
by a uniform pore framework, the relative molecular uptake
and release obey the following equation521,522
∞
m(t ) 6 exp( −i 2π 2DTt /R2)
=1− 2 ∑
m(∞ ) π i=1
i2 (1)
where R is the radius of the sample assumed to be a sphere,
and DT is the intraparticle transport.
In the limiting cases of process control by intraparticle Figure 28. (A) Schematic illustration of the effect of pore size on the
diffusion and surface permeation (surface-barrier control523), diffusion of large (red) and small (black) molecules. (B) Effects of
the respective moments (time constants of molecular uptake, pore diameter on molecular diffusivity (D) and of the energy of
release, or exchange) are activation (Ea) on diffusion. Reprinted with permission from ref 412.
Copyright 2014 John Wiley & Sons, Inc.
R2
τdiff =
15DT (2)
where DT is the intraparticle transport diffusivity, α is the
R permeability through the particle surface (“surface barrier”),
τbarr =
3α (3) and R is the radius of the particle assumed to be a sphere.
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Figure 29. Top: schematic representations of different micro-mesoporous structured zeolites. Red arrows indicate the characteristic diffusion length
in a purely microporous crystal. Yellow arrows represent the reduced path lengths in mesoporous zeolites. Bottom: electron micrographs of typical
mesoporous zeolites. (A, B) Zeolite ZSM-5 single crystal prepared by controlled combustion of carbon particles. The inset is the TEM overview of
mesoporous ZSM-5 single crystals. Reprinted with permission from ref 23. Copyright 2000 American Chemical Society. (C, D) Ultrasmall zeolite
EMT crystals with hexagonal morphology synthesized from a template-free precursor suspension at 30 °C for 36 h. Adapted with permission from
ref 279. Copyright 2012 The American Association for the Advancement of Science. (E, F) Single-crystalline mesostructured zeolite nanosheets
with a lamellar structure using a single quaternary ammonium head amphiphilic template. Reprinted with permission from ref 195. Copyright 2014
Macmillan Publishers Ltd.

For purely microporous zeolites, DT in eq 1 refers to the where c is the guest concentration (in moles per unit mass), p
micropore diffusivity Dmicro. is the gas pressure, and R is the universal gas constant. Vmeso,
Equation 1 is also applicable for the microporous zeolites Vmacro, and Vmicro stand for the specific (per sample weight)
with additional (meso- and/or macroporous) transport pores total volumes of mesopores, macropores, and micropores.
when the exchange between the micropores and the transport With eq 2, the introduced transport pores into purely
pores is sufficiently rapid. In this case, DT refers to effective microporous zeolites will improve the mass transport under the
diffusivity DTeff fast-exchange conditions by enhancing the diffusivity DT (eqs 4
DTeff = DTmicro + pmeso Dmeso and 5).
(4) Therefore, mass transport in hierarchically porous materials
is highly dependent on the rate of mass exchange between
DTeff = DTmicro + pmacro Dmacro (5) these pore spaces. It is determined by the permeability of the
where Dmeso and Dmacro stand for the meso- and macropore interface between these spaces and by the hierarchy factor13
diffusivity (with the first-order estimate as given by eqs 6−7) defined as (Vmicro/Vtotal) × (Smeso/Stotal(BET)), where the
estimated by the Knudsen relation521,524,525 mesopore surface area represents the interface between
mesopore and micropores. Increasing hierarchy factors are
d 8RT known to result in increasing catalytic performance.13,412
Dmeso = As discussed above, the interconnected hierarchy between
3τ πM (6)
the transport pores (meso- or macropores) and the micropores
d 8RT allows for the accelerated intracrystalline diffusion.
Dmacro = As a consequence, the spatial arrangement of the introduced
3τ πM (7)
larger pores is of key importance. The introduction of two or
where d is the mean pore diameter, R is the gas constant, and three levels of porosities in microporous zeolites with the
M is the molar mass. The tortuosity factor τ considers the interconnected hierarchy offers an effective solution to achieve
extension of the diffusion pathways by the pore space a faster mass transfer in the zeolite framework, in which the
tortuosity and is typically of the order of 2−4.521,526−528 macropores provide an unimpeded transport path, and the
pmeso and pmacro are the relative amount of molecules in the mesopores provide a fast pathway for mass transportation and
transport (meso- and macro-) pores and can be estimated as529 enhanced micropore accessibility, thus preventing the further
conversion of reactants into undesirable side products (coke
pVmeso 2 precursors) and thereby extending catalyst lifetime.
pmeso ≈
cVmicroRT (8) Table 1 summarizes the different strategies employed for
different zeolites and structures with hierarchical porosity.
pVmacro 2 Different geometries with isolated voids imbedded in the
pmacro ≈ zeolites and open pore channels through the whole zeolite
cVmicroRT (9) crystal are obtained according to the in situ or postsynthesis
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approaches, thus leading to notably different mass transfer
patterns. It is still a great challenge to achieve an optimized
porous hierarchy within zeolites.384,530−533 To take full
advantage of hierarchically porous structure in a catalytic
reaction, it is important to maximize the interconnectivity
among pores of multilevels. Thus, the fabrication of hierarchi-
cally porous zeolites needs an elaborated design that aims both
at creating abundant meso- and/or macropores and at
guaranteeing their interconnectivity within the microporous
structure without compromising intrinsic properties of zeolites.
Generally, hierarchically structured porous zeolites are divided
into three groups based on the additional pore size, namely,
micro-mesoporous zeolites (containing micropores and mes-
opores), micro-macroporous zeolites (containing micropores
and macropores), and micro-meso-macroporous zeolites
(containing micropores, mesopores, and macropores). This
section presents some concrete examples on how to select and
how to combine different preparation strategies described
above in section 2 to fabricate each type of hierarchically
structured zeolites.
3.1. Micro-Mesoporous Structured Zeolites
Extending the catalytic applications of the microporous zeolites
to bulky organic molecules has long been a driving force for
study aimed at mesoporous zeolites. Mesoporous zeolites
combine the advantages of both the inherent crystalline
structure of the microporous zeolite and an additional
connected or disconnected, ordered or disordered, inter- or
intracrystalline mesopore system. The introduced mesopores
result in the exposure of a larger fraction of the highly acidic
zeolite surface, thus making more pore openings accessible to
the bulky reactants and further improving the already highly
valued catalytic capabilities of microporous zeolites. The
synthesis of mesoporous zeolites can be achieved either by
introducing an additional pore system into zeolite single
crystals, either during the crystallization process of the zeolite
crystal or in an already synthesized microporous zeolite
(intracrystalline mesopore, Figure 29A), or by a purposeful
aggregation of individual zeolite nanocrystals or nanosheets
(intercrystalline mesopore, Figure 29C,E).
3.1.1. Disordered Micro-Mesoporous Structured
Zeolites. Many different strategies exist for tailoring the
mesopore structure within zeolites to meet specific goals. The
diversity of available approaches is discussed in section 2.
Among them, the in situ templating synthesis is currently the
most widely used method because of its versatility. The
templating method is based on the addition of mesopore-scale
hard and soft templates or supports into the synthesis mixture
of microporous zeolites. The amount, size, distribution, and
interconnectivity of the secondary porosity created in the
microporous zeolites are directly related to the space occupied
by the templates. This method can be applied to different
zeolite structures with high yields and is especially suitable for
preparing mesoporous zeolites with high zeolitic character and
a large amount of introduced mesopores. However, the main
drawback of this method is the difficulty of scaling-up due to
the fact that the templates must be removed either by
calcination (for organic templates) or by dissolution (for
inorganic templates) under severe conditions after the
crystallization process. For example, the high temperature
during the calcination process can cause a strong damage of
the zeolite crystalline structure.
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The postsynthetic selective extraction of specific framework
constituents (Al atoms or Si atoms) of the presynthesized
microporous zeolite is another direct approach to prepare
mesoporous zeolites. Obviously, these postsynthetic methods
are not limited to the microporous zeolite systems to form
mesoporous zeolite crystal but are also applied to introduce an
additional mesoporosity in already mesoporous zeolite. These
procedures are indeed destructive processes to scarify part of
the as-synthesized zeolite crystals for creating larger meso-
pores. Thus, the main drawback of these methods is the
dissolution and the great loss of the zeolite mass (up to 40%
weight). The high-temperature steaming534 and acid leaching
techniques for removal of Al-atoms are widely used for zeolite
Y,535 mordenite, Beta, and ferrierite. The resultant mesoporous
zeolites always exhibit low pore interconnectivity, disordered
intracrystalline mesopore structure, and partial collapse of the
microporous structure due to the relative uncontrollability of
the treatments. For example, the steam-created mesopores in
ultrastable Y (USY) are mainly isolated rather than
interconnected and, hence, could not improve the diffusion
of large molecules.306 In addition, dealumination usually leads
to an obvious change in Si/Al ratio and thus the acidity of the
zeolites. Alternatively, desilication is more appropriate for
creating an interconnected mesopore system. Basic media is
used for the postsynthetic treatment to preferentially remove
the framework silica atom from a given zeolite framework. This
approach has been applied successfully to many zeolite
topologies, such as MFI,339 MTW,315 MOR,316 BEA,317
AST, 318 FER, 319 MWW, 320 IFR, 321 STF, 322 CHA, 323
FAU,324,536,537 TON,325 and TUN.538 However, its effective-
ness strongly depends on the Si/Al ratio of the original
zeolites. The presence of a high concentration of negatively
charged AlO4− tetrahedra tends to stabilize the Si species,
preventing its extraction from the framework. Contrarily, the
silica-rich zeolites suffer from uncontrolled and excessive
silicon atom extraction, resulting in wide pore-size distributions
and extremely low yields. Besides, the desilication process
usually leads to deposition of partial Al species on the external
surface of zeolites and thus negatively affects the catalytic
performance.539
Another type of mesoporous zeolite is the aggregate of
zeolite nanocrystals/nanosheets. These aggregates are ideal
candidates to facilitate mass transport based on their
interconnected secondary pore system, large external surface
areas, and short intraparticle diffusion pathways (Figure
29C,D).157,540 Hierarchically porous zeolites aggregated by
nanocrystals can be prepared by the assembly and
condensation of zeolite nanocrystals around surfactant
micelles. This includes the use of common templates under
specific synthesis conditions that favor nanozeolite growth.
Seed-induced synthesis, multiple-step pretreatment, additive-
assisted crystallization, and a controlled crystalline process are
often used. The use of uncommon structure-directing agents,
such as cyclic or linear diamino- or diamine structure-directing
agents, under a common synthesis condition, or the self-
assembly is also an applicable method to form larger and
mechanically stable aggregates avoiding using a mesopore
template. Hierarchically porous zeolites aggregated by nano-
sheets can be obtained by postsynthesis (Figure 29E,F), such
as swelling,346−348 exfoliating,342,349 or interlayer pillaring with
amorphous silica,350−352 or in situ synthesis, such as soft
template synthesis which was successfully applied to the
synthesis of layered aluminosilicates157,158 and aluminophos-
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Figure 30. TEM images and inset diffraction patterns of (A) the 3DOm carbon template with a pore size of ca. 20 nm and (B) confined Silicalite-1
crystal growth carried out in a 20 nm 3DOm carbon template. Reprinted with permission from ref 48. Copyright 2008 Nature Springer. High-
resolution SEM (C) and TEM (D) images of the ordered multilamellar MFI zeolite nanosheets, in which the interlayer spacing has been supported
with silica pillars. These images were taken after calcination. White arrows in parts C and D indicate the silica pillars between the zeolite
nanosheets. Reprinted with permission from ref 158. Copyright 2010 American Chemical Society.

Figure 31. Top: schematic representation of different micro-macroporous structured zeolites. Bottom: electron micrographs of typical
macroporous zeolites. (A, B) Hollow zeolite capsules through the vapor phase transport treatment of the nanozeolite coated MS sphere templates.
Reprinted with permission from ref 111. Copyright 2002 American Chemical Society. (C, D) ZSM-5 hollow microboxes prepared by desilication in
mild alkaline media. Reprinted with permission from ref 541. Copyright 2008 The Royal Society of Chemistry. (E, F) Macroporous zeolite single
crystal using mesoporous silicas as templates. Reprinted with permission from ref 120. Copyright 2014 John Wiley & Sons, Inc.

phates.161 These intercrystalline mesopores are unstable and
can be easily destroyed when treated under high stress. It is still
a great challenge to improve the structural stability of the
zeolite nanocrystal aggregates.
3.1.2. Ordered Micro-Mesoporous Structured Zeo-
lites. All of the aforementioned mesopores are often
disordered in hierarchically porous zeolites. Generally, an
interconnected and three-dimensionally ordered mesopore
system is introduced into zeolites during the crystallization
process. Additionally, the precise control over the ordered
mesoporous structure in these zeolites is difficult to achieve. In
this subsection, we select the strategies and methods to realize
pore interconnectivity (ordered mesopores).
The most straightforward technique for constructing an
ordered mesoporous structure within zeolites is the replication
in ordered porous structures produced by templated synthesis
using colloidal assemblies. The general idea for these
replications is to partially or fully replicate the preformed
sacrificial templates which direct the final structures. Addition-
ally, morphological characteristics of the mesopores can be
precisely controlled. The diameter of the mesopores in
3DOM/m materials can be tuned by altering the size of the
original colloidal spheres. For example, Tsapatsis and his co-
workers prepared microporous zeolites with ordered meso-
porosity by using three-dimensionally ordered mesoporous
(3DOm) carbons with a face-centered-cubic structure as hard
templates (Figure 30A).48,49 The confined growth of Silicalite-
AL
1 zeolite crystals in these templates afforded 3DOm-imprinted
single-crystal zeolite particles, which showed a network
particulate structure consisting of primary nanoparticles
(about 10, 20, or 40 nm in diameter) (Figure 30B). A wide
range of crystal morphologies can be imprinted into zeolite
crystals by replication of size-tunable mesoporous carbon
templates.48 Moreover, this novel method can be applied to
synthesize not only the aforementioned Silicalite-1 zeolite but
also many other types of zeolites, like BEA, LTA, FAU, and
LTL.49 Collectively, the 3DOm structure endows zeolites with
a highly ordered pore system and thus promises a fluent mass
transport ability, which is useful in various applications like
catalysis, sensing, and adsorption−separation.
The soft templating method is another conventional and
general method for the synthesis of ordered micro-mesoporous
structured zeolites. The diameter of the mesopores can be
tuned by changing the surfactant. Additionally, the pores can
be aligned perpendicular or parallel to the surface of the
spheres. For instance, Ryoo and his co-workers prepared a
functionalized surfactant and used it as a structure-directing
agent (SDA) to synthesize zeolite MFI nanosheets with a
thickness of 2 nm by the hydrothermal method.158 The
surfactant tails outside these obtained zeolite nanosheets direct
their further aggregation into an ordered mesoporous multi-
lamellar structure. Moreover, the diameter of interlayer
mesopores can be controlled by tuning the surfactant tail
length. Notably, the mesopores between zeolite nanosheets can
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be preserved by using silica pillars, even after surfactant
removal (Figure 30C). In addition, it was observed that some
paralleled zeolite nanosheets have single-unit-cell (Figure
30D). The pillared zeolite with a hierarchically ordered
mesoporous structure possessed many advantageous features,
like an ordered micro-mesoporous structure, large surface area,
abundant pore volume, highly accessible acid sites, and tunable
interlayer mesopores.158 The hierarchically ordered meso-
microporous zeolites will offer a short diffusion path during
catalytic reactions, especially when large molecules are
involved.
As a result of the numerous templating approaches that have
been developed in past decade, researchers now hold in hand a
vast choice of synthesis methods to construct micro-macro-
porous structured zeolites. More importantly, the in situ
approach including hard and soft templating methods can
produce ordered micro-mesoporous zeolite materials, which
are very hardly obtained with postsynthesis methods. These
ordered micro-mesoporous zeolites have the maximized
connectivity between pores of various levels and can fully
realize the benefits of hierarchy in catalytic reactions.
3.2. Micro-Macroporous Structured Zeolites
Macroporous zeolites constitute another important category of
hierarchically porous zeolites. The introduction of a macro-
porous structure into a microporous zeolite results in a
reduced diffusion path, accelerated mass transfer, and increased
coke resistance in catalytic reactions. Many efforts have been
devoted to synthesize macroporous zeolites. Various morphol-
ogies, such as hollow spheres (Figure 31A),101 fibers,145 and
boxes (Figure 31B);541 macroporous zeolite single crystals
(Figure 31C);120 and three-dimensional (3D) hierarchically
macrostructured monoliths, were obtained.
The in situ templating method is an effective method to
synthesize macroporous zeolites. Polymer spheres97,99,430 or
silica spheres111,114,115 and other special materials, such as
hydrothermally pretreated carbon black microspheres,542
hydrothermally pretreated micron-sized carbon fibers,543−547
the fly ash cenosphere,124 silica-containing vegetal cells,137 and
CaCO3,548 are widely used to template hollow macroporous
structures in the zeolites. The final morphologies of the hollow
structure in macroporous structured zeolites can be easily
controlled by changing the initial template morphologies.118
For example, most of the methods for preparing macroporous
zeolite with a hollow sphere structure are based on a layer-by-
layer assembly technology. This includes the first alternative
deposition of oppositely charged zeolite nanoparticles and
polyelectrolytes onto the polymer spheres97,99,430 or silica
spheres111,114,115 to form a core−shell composite followed by
the removal of the template core to fabricate a hollow
structure. Macroporous zeolites with a hollow fiber structure
are synthesized by incorporating bacterial supercellular threads
into the as-synthesized silicalite nanoparticles.145
The self-assembly of the uniform spherical templates
mentioned above can also be used to fabricate zeolite
monoliths with closed or interconnected macropores.112,113,117
Indirect templating involving both the inert support and the
active support can also be used to synthesize macroporous
zeolite monoliths. Inert supports are divided into permanent
inorganic supports and sacrificial supports. In a typical
synthesis, the microporous supports are immersed into the
zeolite precursor solution, and then, the mixture is crystallized
via a conventional one-step hydrothermal method. The
AM
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synthesized zeolite nanocrystals are either loaded onto or
coated onto the surface of these supports after impregnating
the supports into the zeolite precursor solution. Different
micro-macroporous zeolite monoliths are prepared by
choosing various inert supports, such as diatoms,430 porous
Al2O3 beads/extrudes,549 silicon oxycarbide (SiOC) ceramic
foams,223,550 ZrO2/Y2O3,421 cordierite honeycomb,551 and
stainless steel.422 Sacrificial supports, including natural
templates (bacterial supercellular threads,145 starch gels,147
wood cells,139,141 egg membranes131) and artificial templates
(polyurethane foam, PUF106), are also used to prepare
hierarchically micro-macroporous zeolite monoliths. The
resultant materials exhibit a diverse hierarchical structure but
a relatively low mechanical stability. To further improve the
mechanical stability, macroporous supports containing the
initial nutrients for the zeolite growth, such as active silica or
alumina, are used.135,434−439,441−443 After the complete or
partial crystallizations, binder-free hierarchically porous
zeolites or partly zeolite materials with hierarchical macro-
porous supports are obtained. Thus, the resultant macroporous
zeolites exhibit a high mechanical stability owing to the strong
interaction between zeolite nanocrystals or zeolite coatings and
supports.
Mesoporous silica spheres120 and other templates, such as
nanosized CaCO3,121 can also be used as hard templates to
introduce intracrystalline macropores in zeolites. For example,
the MFI-type zeolite single crystal with a classical morphology
and well-interconnected intracrystalline macropores can be
prepared using mesoporous silica spheres as both a silica
nutrient and a sacrificial macropore porogen. Intracrystalline
macropores that are connected to the crystal external surface
are formed after the crystallization process by the sacrifice of
silica particles (Figure 31E,F).120
The in situ nontemplating route can also be used to prepare
macroporous zeolites with a hollow sphere structure. For
example, Silicalite-1 zeolite nanocrystals with a size less than 30
nm are self-assembled to form hollow spheres with a diameter
of 100−300 nm after sonication in an ammonia−ethanol
solution.286
The postsynthesis desilication process is also an efficient
methodology to construct hollow micro-macroporous zeolite
architectures. For example, macroporous zeolite with a hollow
microbox structure are prepared by treating the high-quality
ZSM-5 zeolite single crystal in a mildly alkaline Na2CO3
solution, avoiding the excessive destruction of ZSM-5 zeolite
crystals (Figure 31C,D).541 Besides, the postsynthetic
recrystallization approach is also developed for the preparation
of macroporous zeolite TS-1552 and microporous zeolite ZSM-
5553 with hollow structures.
3.3. Micro-Meso-Macroporous Structured Zeolites
Most reported hierarchically porous zeolites contain either
mesopores or macropores. However, hierarchically porous
structured catalysts with both mesopores and macropores are
more desirable in catalytic applications. Nowadays, it is still
highly challenging to simultaneously create both mesopores
and macropores within zeolites. Until now, only a few micro-
meso-macroporous zeolites with pores at three length scales
are reported.
The in situ direct template method can be used to obtain
hollow SAPO-34 zeolite nanocrystals with intracrystalline
meso-macropores. The catalysts are prepared via the seed-
assisted crystallization using triethylamine as the sole structure-
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Figure 32. (A) Left: schematic representations of hierarchically micro-meso-macroporous zeolites synthesized via a quasi-solid-state crystallization
approach. Right: pore-size distributions of the micropores, mesopores, and macropores in hierarchically micro-meso-macroporous Beta zeolites
(MMM-Beta), calculated by the HK method, the BJH method, and Hg intrusion porosimetry, respectively. (B) SEM and (C) TEM image of
MMM-Beta. The inset in part C is the corresponding selected area electron diffraction (SAED) pattern taken from many nanocrystals. Adapted
with permission from ref 235. Copyright 2011 John Wiley & Sons, Inc. (D) Schematic representations of the hollow nanovesicle assembly with the
hollow Fe2O3-encapsulated MFI-type nanocrystal (Fe2O3@hier-ZSM-5). (E, F) TEM images of Fe2O3@hier-ZSM-5. The inset in part F is the
SAED patterns of Fe2O3@hier-ZSM-5. Adapted with permission from ref 555. Copyright 2016 American Chemical Society.

directing agent. The samples exhibited a hollow structure with
mesopores and macropores throughout the entire crystals.554
The in situ indirect templating route is usually used for the
synthesis of meso-macroporous zeolites. For example, a
complete zeolitization of bimodally porous silica monoliths
with a hierarchically meso-macroporous structure is an
effective method to prepare various hierarchical zeolites with
micro-meso-macroporous structures. For example, hierarchi-
cally porous Silicalite-1,231 ZSM-5,108 and Beta240 zeolite
monoliths are obtained by the transformation of the bimodally
porous silica skeleton through a steam-assisted conversion.
Thus, the sodalite233 and SAPO-34236 zeolite monoliths with a
hierarchical pore can be prepared by a pseudomorphic
transformation of the meso-macroporous silica monolith233
or a dry-gel conversion of amorphous silico aluminophos-
phate.236
The connectivity between the various levels of pores in
hierarchical zeolites is the key to maximize the benefits of
hierarchy in catalytic reactions. An ideal hierarchically porous
catalyst should contain well-defined macropores, intercon-
nected and uniform mesopores within the macropore walls,
and tunable microporous zeolite units. To realize this, a novel
glycerol-assisted quasi-solid-state crystallization (QSSC) proc-
ess was used to synthesize hierarchically micro-meso-macro-
porous zeolites.237 All pores were introduced throughout the
entire product to give highly interconnected macrochannels
with uniform mesopores and micropores (Figure 32A−C). By
using this method, a series of hierarchically micro-meso-
macroporous zeolites have been synthesized.234,235,237,242
AN
Hierarchically micro-meso-macroporous MFI-type zeolites,
with a core−shell architecture composed of a nonporous core
and an epitaxially grown hyperbranched shell full of mesopores
and macropores, were prepared by an in situ nontemplating
two-step controlled crystallization process.275 The first step
was synthesized at low temperatures (20−80 °C), and most
precursors hydrolyzed and condensed to obtain precrystallized
clusters, which further aggregated in an oriented order at
medium temperatures (100−140 °C) during the second
synthesis step. The branching epitaxial growth due to
aluminum-zoning resulted in the synthesis of the hierarchically
porous zeolites.
The postsynthetic recrystallization can be used to prepare
metal-encapsulated hollow zeolite nanocrystals. The synthesis
consisted of two steps. First, a template-free hydrothermal
synthesis of hollow aggregates of metal-containing zeolite
nanocrystals was realized, and then, a selective desilication−
recrystallization together with a leaching−hydrolysis was
performed to transform the metal-containing zeolites into
metal-encapsulated hollow zeolite crystals. The obtained
material was found to possess a microporous (0.4−0.6 nm)
wall of hollow zeolite crystals and a mesoporous (5−17 nm)
shell of a nanovesicle with macropores of about 350 nm in the
core (Figure 32D−F).555
In conclusion, hierarchically porous zeolites available today
can be divided according to the size range of the additional
porosity from micro-mesoporous structured zeolites, micro-
macroporous structured zeolites, and micro-meso-macro-
porous structured zeolites, in which the secondary porosity
can be found either within the zeolite crystals or in the
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Figure 33. Overview of the catalytic applications of hierarchically porous zeolites.
intercrystalline voids. Numerous preparation methods are
applied for hierarchically porous zeolites (Table 1). However,
the underlying synthetic principles are simple, which are
crystallization, aggregation, and extraction.130 Hierarchically
porous zeolites can be prepared by using a single principle or a
combination of two or three principles during the synthesis
process.
4. APPLICATIONS
4.1. Catalytic Application
The introduction of meso- or macropores into microporous
zeolites can significantly accelerate the mass transport, reduce
the diffusion path of the reactants, and improve the
accessibility of reactants to and the escape of products from
the catalytic active sites in the catalytic reaction, leading to an
increased reactant conversion/product selectivity and an
extended lifetime of catalysts.556,557 Therefore, hierarchically
structured porous zeolites are quite desirable for catalysis and
other processes.9,558,559 In this section, we illustrate the
abundant catalytic applications of hierarchically porous zeolites
as catalysts in various reactions and show how the hierarchical
porosities in zeolites can improve the catalytic properties of
parent zeolites. Figure 33 and Table 2 give an overview of the
catalytic applications of hierarchically porous zeolites.
4.1.1. Friedel−Crafts Reaction. 4.1.1.1. Friedel−Crafts
Alkylation of Arenes. The liquid-phase catalytic conversion of
bulky molecules mainly takes place on the external surface of
microporous zeolites and is an important probe reaction to
evaluate the structural advantages of hierarchical zeolites. The
Friedel−Crafts (F−C) alkylation is one of the most important
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approaches to produce value-added aromatic compounds in
industry via the formation of new carbon−carbon bonds
between aromatic hydrocarbons and other aromatic agents.726
Among these alkylations, the benzylation of aromatic hydro-
carbons (benzene, 162,574,576 toluene, 577 and mesity-
lene,249,409,560,561,575,578 etc.) with benzyl alcohol (BA) or
benzyl chloride (BC) in the liquid phase can produce
diphenylmethane and substituted diphenylmethanes, which
are important intermediates widely used in pharmaceuticals,
petrochemicals, fine chemicals, dyes, and many other
chemicals.727 These reactions can be catalyzed by Lewis or
Brønsted acids. Zeolites, such as H-ZSM-5,562,563 H-Beta,564
HY,565 and H-SAPO-5,566 have been widely used in
benzylation reactions due to their strong acidity, shape
selectivity, and high hydrothermal/chemical stability. However,
microporous zeolites are less active and deactivate rapidly in
the benzylation of bulky reactants due to their relatively small
micropore size.567−570 Besides, as the contacting time of the
reactants with the catalysts increases, further alkylation and
isomerization of the alkylated products can occur. Poly-
alkylation, isomerization, transalkylation, dealkylation, and
polymerization are all the possible side reactions under the
normal reaction conditions. Thus, it is very important to
choose appropriate catalysts to decrease these side reactions.
Christensen et al.563 demonstrated that the mesoporous zeolite
catalyst had higher benzene conversion (18% vs 15%) and
higher selectivity to ethylbenzene (83% vs 74%) than
conventional zeolites in the catalytic alkylation of benzene
with ethene, although the conventional zeolite catalyst had
almost twice as many acidic sites as the mesoporous zeolite
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Table 2. Catalytic Reactions Employed over Hierarchical Zeolites

Figure 34. (A) Schematic representations of the F−C alkylations taken at the external active sites and internal active sites of zeolites. (B, C)
Conversion of benzyl alcohol over bulk Beta, nano-Beta, nano-Beta with external-acid poisoning by triphenylphosphine, and nano-Beta with
micropore blocking by coke, plotted as a function of reaction times: 0−1 h (B) and 0−120 h (C). Adapted with permission from ref 574. Copyright
2014 Elsevier.

catalyst. This activity difference can be attributed to improved
mass transport in the mesoporous zeolite. Thus, hierarchically
porous zeolites could be the ideal catalysts for the F−C
alkylation involving large molecules due to the facile diffusion
AP
through the meso-macropores, high stabilities, low apparent
activation energy of the crystalline zeolite frameworks, and easy
accessibility of acid sites to bulky reactants.329,571,572
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Figure 35. Morphology and Friedel−Crafts catalytic alkylation properties of the pure-silica self-pillared pentasil (SPP) zeolite particles. (A)
Schematic representation of benzylation of mesitylene (MES) with benzyl alcohol (BA). (B) High-resolution TEM image of an SPP lamella viewed
across its thin dimension; the FFT from the lamella is consistent with the [010]-zone axis of zeolite MFI. (C) Plots for rate constant and selectivity
determination for mesitylene alkylation reactions over zeolite catalysts: 1.4 μm commercial MFI, 3DOm-i MFI, pillared MFI and SPP (Si/Al =
253). Reproduced with permission from ref 573. Copyright 2012 The American Association for the Advancement of Science.

4.1.1.1.1. F−C Alkylation Using Benzyl Alcohol (BA) as the
Aromatic Agent. A hexagonally ordered mesoporous molec-
ular sieve with a 1.7 nm thick wall of crystalline MFI-like
microporous framework exhibited much higher catalytic
conversion (44 wt %) in alkylation of benzyl with benzyl
alcohol than both conventional Beta zeolite (19 wt %) and
ordered mesoporous amorphous materials Al-MCM-4 (8 wt
%).162 This was due to the abundant accessible external acid
sites in the as-synthesized mesoporous molecular sieves, as
compared with Al-MCM-41 or conventional zeolite Beta. The
acid number was characterized by titration of the zeolites using
triphenylphosphine oxide (TPPO) as the probe molecule while
the acid strength was measured by 31P magic angle spinning
nuclear magnetic resonance (MAS NMR).728,729 The bulky
TPPO molecules are too large for the 12-member-ring
micropores and thus can only reach the external acid sites
on the mesopore surfaces. It was found that the 31P NMR
chemical shift of TPPO increased with increasing binding
affinity toward Brønsted acid sites.728 The crystalline
mesoporous molecular sieves titrated with TPPO exhibited
31
P NMR signals up to 55.7 ppm compared with 44.3 ppm for
Al-MCM-41, indicating that the mesoporous molecular sieves
exhibit stronger acid sites than Al-MCM-41. Conventional
zeolite Beta also showed NMR signals up to 55.7 ppm, but the
amount of the strongest external acid sites was less than that of
crystalline mesoporous molecular sieves. When the meso-
porosity was introduced into bulky Beta zeolite resulting in the
formation of mesoporous Beta zeolite with a nanosponge
morphology, improved catalytic turnovers and extended
lifetime in benzene alkylation with benzyl alcohol were
observed.574 The benzene conversion remained as high as 80
wt % even after 50 h. In contrast, the purely microporous Beta
zeolite gave a benzene conversion of less than 20 wt % and
deactivated rapidly after about a 10 h reaction (Figure 34).
The high catalytic performance was attributed to the higher
concentrations of accessible external acid sites on the large
accessible surface due to the introduction of mesopores in the
AQ
Beta zeolites. The 31PMAS NMR measurements proved that
the quantity of the strongest external acid sites of mesoporous
molecular sieves is much larger than that of bulky Beta
zeolites.162 These accessible active sites could catalyze the
alkylation reactions even after active sites inside the zeolite
micropores were deactivated. Similar results were observed for
hierarchically porous zeolites with other morphologies, such as
MFI nanosheets, MTW nanosponge, and MRE nanosponge.574
Li et al.576 prepared a series of hierarchically mesoporous
mordenites by three different methods, which are acid leaching
followed by base leaching (the samples HMOR-A1 treated
with 72 mL of 0.2 M NaOH and HMOR-A2 treated with 87
mL of 0.2 M NaOH), soft templating using [3-
(trimethoxysilyl)propyl][hexadecyldimethylammonium] chlor-
ide (the sample HMOR-TPHAC), and hard templating using
carbon black (the sample HMOR-carbon). The HMOR-A1
and HMOR-A2 had highest BET surface area (524 vs 530 m2
g−1), which are 1.4 times higher than that of H-mordenites
(378 m2 g−1) and 1.7 times higher than that of HMOR-carbon
(317 m2 g−1). They further compared their catalytic perform-
ances in the liquid-phase alkylation of benzene with benzyl
alcohol. The conversion of benzyl alcohol over HMOR-A1 and
HMOR-A2 was near 100% after 3 h, but the conversion of
benzyl alcohol on HMOR-TPHAC and HMOR-carbon was
less than 3%. This was because diphenylmethane which was
formed has a large size, and the conventional mordenite does
not provide enough space for this molecule to diffuse through
the micropores while the introduced mesopores enabled
diphenylmethane to escape from the mordenite crystal.
Compared with benzene, toluene has a larger molecular size
of 0.54 nm. Its alkylation with benzyl alcohol over hierarchi-
cally mesoporous mordenites and microporous mordenites
confirmed the superiority of the introduced mesopores.577
Hierarchically porous mordenites were prepared by a
sequential post-treatment method based on a commercial
mordenite with a Si/Al molar ratio of 15.577 The hierarchically
porous mordenites with acid−base−acid treatment (HM-
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Figure 36. (A) Various ZSM-5 catalysts with different degrees of mesoporosity prepared by different synthesis methods. (B) Benzylation of
mesitylene (MES) with benzyl alcohol (BA) over various ZSM-5 catalysts. Adapted with permission from ref 560. Copyright 2012 Elsevier.
ABA) had a mesopore volume of 0.32 cm3 g−1, which was
three times higher than that of the parent mordenite (0.10 cm3
g−1). The HM-ABA also had the highest external surface area
(119 m2 g−1), which was more than 3 times higher compared
with that of H-mordenites (36 m2 g−1) and more than twice
compared with that of acid-leached mordenite (49 m2 g−1) and
acid−base-leached mordenite (58 m2 g−1). The results
indicated that the acid-washing after base treatment can
significantly increase the external surface area of the samples,
which resulted from the complete removal of the deposited
aluminum species from the framework. The high mesopore
volume and external surface area of HM-ABA led to more
accessible acid sites and accelerated mass transport. The
apparent reaction rate constant for acid−base−acid-leached
mordenite (HM-ABA) was 15 times higher than that for H-
mordenite and twice those of acid-leached mordenite and
acid−base-leached mordenite.577
Mesitylene has a kinetic molecular diameter of 0.87 nm,
which is much larger than the entrance size of micropores in
zeolite ZSM-5. Therefore, these bulky molecules cannot
penetrate into the inner microchannels of ZSM-5, and the
alkylation can happen only on the accessible external surface of
the catalyst.383 The introduction of meso- or macroporosity
into microporous zeolites can facilitate the access of mesitylene
to more active centers and thus leads to excellent catalytic
conversions. Besides, the amount of accessible acid sites is the
determinant of the product selectivity since the desired
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alkylation of benzene to 1-benzyl-2,4,6-trimethylbenzene
cannot take place in the micropores whereas the side
etherification of benzyl alcohol to dibenzyl ether can.730 The
base treatment of microporous Beta zeolites can significantly
increase the accessible framework surface area and thus the
number of accessible framework Brønsted acid sites. The
hierarchically porous Beta zeolites prepared by base treatment
exhibited excellent catalytic properties and remarkable product
selectivity in the benzylation of mesitylene.575 Zhang et al.573
synthesized self-pillared pentasil (SPP) zeolite by an MFI/
MEL intergrowth and used it in mesitylene alkylation (Figure
35A). The orthogonally connected nanosheets created a
permanent network of mesopores (Figure 35B).158 Such
nanometer-scale diffusion lengths offered fast transport even
for molecules with a small micropore diffusivity. The catalytic
properties of SPP zeolites at Si/Al of 253 were compared with
those of pillared MFI prepared by hydrothermal synthesis via
the cooperative assembly between silica and an organic
surfactant functionalized with a diquaternary ammonium
group,158 three-dimensionally ordered mesoporous-imprinted
(3Dom-i)) MFI, and three conventional MFI zeolite catalysts
with a crystal size of 1.4 μm. The number of accessible acid
sites was determined by a titrant molecule, 2,6-ditert-
butylpyridine (DTBP), which cannot enter the zeolite
micropores. Specifically, 30% and 45% of the acid sites in
pillared MFI and SPP, respectively, were accessible by a
molecule that cannot penetrate into the internal micropores.
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Figure 37. Morphology and Friedel−Crafts acylation catalytic properties of the hierarchical Beta zeolite nanocrystals. (A) TEM image of the
hierarchical Beta zeolite nanocrystals with HTEM image inset. (B) Comparison of p-methoxyacetophenone (p-MAP) over hierarchical Beta,
traditional, and commercial Beta zeolites in the acylation of anisole with acetic anhydride. Adapted with permission from ref 579. Copyright 2017
Elsevier.
But only 2% of acid sites were accessible in a micrometer-sized
zeolite crystal. Due to these more accessible acid sites, the
pseudo-first-order rate constant for the alkylation of bulky
mesitylene by benzyl alcohol increased by more than 2 orders
of magnitude (Figure 35C). Jin and co-workers409,560 system-
atically investigated the influence of mesopores on product
selectivity in the benzylation of mesitylene over different ZSM-
5 catalysts with various mesoporosities. Mesoporous ZSM-5
zeolites were obtained by the assembly via ionic interaction
between sulfonic-acid-functionalized or nonfunctionalized
ZSM-5 zeolite nanocrystals and counter cationic surfactant
CTAB under microwave [Meso ZSM-5 (SO3H-CTAB)-MW
and Meso ZSM-5 (CTAB)-MW] and hydrothermal synthesis
[ZSM-5 (SO3H-CTAB)-HT] and ZSM-5 (HT)] (Figure
36A). Whichever synthesis treatment is used, the sulfonic
acid functionalizations of zeolite crystals led to a large surface
area and porous volume while microwave treatment induced
mesoporosity. The surface area SBET and mesopore volume
Vmeso varied as Meso ZSM-5 (SO3H-CTAB)-MW (529 m2 g−1
and 0.75 cm3 g−1) > Meso ZSM-5 (CTAB)-MW (500 m2 g−1
and 0.35 cm3 g−1) > ZSM-5 (SO3H-CTAB)-HT (388 m2 g−1
and 0.21 cm3 g−1) > ZSM-5 (HT) (348 m2 g−1 and 0.11 cm3
g−1), while the acid strengths were found to be approximately
similar to the conversional ZSM-5 [ZSM-5 (HT)].409,560 The
external acid sites in mesoporous ZSM-5 were more accessible
for the guest molecules, leading to a nearly 5-fold increased
catalytic activity than that of microporous ZSM-5 in the
aromatic benzylation (Figure 36B).409,560 The selectivity of
desired monobenzylated aromatic molecules was determined
by the degree of mesoporosity. As a result, mesoporous zeolite
ZSM-5 with the larger mesopore volume exhibited increased
selectivity toward the desired bulky monobenzylated aromatics
than those of microporous ZSM-5, which had dibenzyl ether as
a major product due to the diffusion limitation.
4.1.1.1.2. F−C Alkylation Using BC as an Aromatic Agent.
Dai et al. prepared hierarchical mordenite zeolite nanorod
bundles by using organosilane functioned fumed silica as the
silicon source.578 The organic moiety linked on the surface of
fumed silica inhibited the growth of zeolite crystal into a large
size, leading to the assembled nanorod bundles. Samples
prepared by organosilane functioned fumed silica with different
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ratios gave different BET surface areas, external surface areas,
and mesoporous volumes.578 The size of mordenite nanorods
decreased as the organic function degree increased, leading to
samples with a higher mesoporous volume (0.15 cm3 g−1) and
larger external surface area (148 m2 g−1). The hierarchical
mordenite nanorod bundles exhibited increased accessible
active sites and thus increased benzylation (78.9 wt %) as
compared with conventional mordenite (13.4 wt %). A similar
phenomenon was observed for the spherical-like self-
assemblies of ZSM-5 nanocrystals with controllable hierarch-
ical architectures, which were prepared by using organo-
functionalized mesoporous silica as the silica source. These
spontaneously stacked nanocrystals had a large accessible
surface area, and therefore, 67% of the Brønsted acid sites were
accessible to bulky molecules. These hierarchical ZSM-5
zeolite nanocrystals showed significantly high benzyl chloride
conversion in the benzylation of mesitylene, and the reaction
rate increased by more than 50 times as compared to that
achieved by conventional ZSM-5.561
4.1.1.2. Friedel−Crafts Acylation of Arenes. The Friedel−
Crafts (F−C) acylation of arenes is an important industrial
process to synthesize aromatic ketones, which are widely
utilized in pharmaceuticals, fragrance products, fine chemicals,
and so on.731 It involves the reaction of an aromatic
hydrocarbon with acylating agents such as acyl chlorides
(ACs) and acid anhydrides (AAs) in the presence of acid
catalyst.732 Recently, economical and ecofriendly heteroge-
neous solid catalysts have gained more attention.733,734 Among
these materials, zeolites exhibit a high activity in F−C acylation
due to their strong acid sites and high stability.735−737 Zeolite
Beta and Y are known to be the most efficient catalysts for the
F−C acylation of aromatic compounds due to their relatively
large 12-membered-ring micropores.582,738 However, they still
suffer from fast deactivation due to the adsorption of heavy
products and the permanent deposition of carbonaceous
substances. This problem can only be solved by introducing
mesopores into the zeolite framework.739 The F−C acylation
of anisole with acetic anhydride produced p-methoxy
acetophenone (p-MAP) and o-methoxy acetophenone. All
the catalysts showed a selectivity >99% for the product p-MAP.
p-MAP yield based on the initial amount of acetic anhydride
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was thus used to compare the catalytic performance.579
Hierarchical zeolite Beta was rapidly synthesized within 4 h
with a high yield using a layered silicate precursor (H-
kanemite) as the silica nutrient (Figure 37A).579 The obtained
hierarchical zeolite Beta consisted of self-sustaining macron-
sized zeolitic aggregates assembled by uniform nanosized
crystals and possessed relatively narrowly distributed inter-
crystalline mesopores around 20 nm with a high pore volume
and external surface area. Their catalytic properties were
investigated in the F−C acylation reaction and were compared
with commercially available or traditional Beta zeolites.
Traditional Beta with Si/Al of 20 (T-Beta-20) and conven-
tional Beta with Si/Al of 20 (C-Beta-20) gave 20% and 30%
yield of p-MAP in 30 min, respectively. It reached 26% and
35% in 1 h, and 33% and 43% in 3 h, respectively. In contrast,
the hierarchical Beta zeolites with Si/Al of 20 (N-Beta-20)
gave an enhanced yield of p-MAP, which reached 45%, 50%,
and 57% in 30 min, 1 h, and 3 h, respectively. The highly
improved catalytic performance of hierarchical Beta zeolite (N-
Beta) was due to eliminated diffusion constraints contributed
by the intercrystalline mesopores (Figure 37B).
Similar results were obtained by Kore et al.580 Hierarchical
Beta zeolites with inter-/intracrystalline mesoporosity ex-
hibited excellent activity and selectivity for the synthesis of a
wide range of aromatic ketones. Generally, conventional MFI
zeolites were not suitable for the F−C acylation due to their
relatively small 10-memberd-ring micropores. To solve this
problem, Kim et al.190 synthesized MFI zeolite nanosponges
with disordered intracrystalline macropores. The abundant
acid sites on the large external surface areas served as excellent
catalytic active centers for the conversion of bulky aromatic
compounds in the acylation of anisole with acetic anhydride.
The hierarchically porous ZSM-5 zeolite thus exhibited a much
higher anisole conversion (>80 wt %) when compared with
micron-sized ZSM-5 crystals (14 wt %), which was attributed
to the improved accessibility of the reactant molecules to the
acid sites and the enhanced diffusion of the reactant/products
through the intercrystalline mesopores.582,583 Yan et al.581
systematically reviewed the catalytic applications of hierarch-
ical zeolites in a series of liquid-phase F−C acylation reactions,
focusing on hierarchical ZSM-5 and Beta prepared by different
methods. The nanohierarchical materials exhibited a higher
catalytic activity than conventional zeolites in all liquid-phase
reactions. The reduced crystal size of nanozeolites in the
hierarchically porous zeolites provided short diffusion channels
and thus increased the conversion rate of the reactants.
Besides, the deactivation rate of nanozeolites was greatly
reduced because the short diffusion path in hierarchically
porous zeolites aggregated by nanozeolites allowed the fast
transport of reactants/products and prevented coke deposition
in the micropores.
The catalytic applications of hierarchical zeolites in the
liquid-phase F−C alkylation and F−C acylation are briefly
reviewed. Hierarchical zeolites are more active and more
selective than the conventional zeolites in these liquid-phase
reactions, thus making them appropriate for the conversion of
a bulky molecule. Moreover, the abundant accessible active
sites are decisive in the liquid-phase reactions. Therefore,
efforts should be made to develop hierarchical zeolite materials
containing both exciting structures and an increased external
surface.
In conclusion, the Friedel−Crafts (F−C) alkylation and the
acylation of arenes are both important approaches to produce
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value-added aromatic compounds in industry. Zeolites are
widely used in the F−C reactions due to their strong acidity,
shape selectivity, and high hydrothermal/chemical stability.
However, conventional zeolites with relatively small micro-
pores are less active and deactivate rapidly in F−C reactions
due to the serious adsorption of heavy products and the
permanent deposition of carbonaceous substances in their
relatively small micropore size. Thus, hierarchically porous
zeolites are the ideal catalysts for F−C reactions involving large
molecules due to the facile diffusion through the meso-
macropores and easy accessibility of acid sites to bulky
reactants.
4.1.2. Beckmann Rearrangement. Zeolites with addi-
tional large pore systems are common strategies to reduce
diffusion limitations in diffusion-controlled catalytic reac-
tions.85 Vapor-phase Beckmann rearrangement reactions are
usually carried out over zeolite catalysts. The introduction of
additional porosity, such as mesoporosity, into zeolites seemed
to be the best choice. The Beckmann rearrangement of
ketoximes into amides is known as a fundamental chemical
reaction in organic synthesis.740 One of the most important
rearrangement reactions used in industry is the conversion of
cyclohexanone and cyclododecanone oximes into ε-caprolac-
tam and ω-laurolactam, which are widely used as raw materials
for the production of polyamides such as nylon-6 and nylon-
12.584 Hierarchically porous (HP) SAPO-34 zeolite was
synthesized by a one-pot soft templating method using
dimethyl octadecyl[(3-(trimethoxysilyl)propyl] ammonium
chloride (DMOD).585 The rodlike mesopores were inter-
connected within the micropores. The HP SAPO-34 contained
both isolated weak Brønsted acid sites (red diamond, Figure
38A) and silanol sites within the mesopores (blue circle and
square, Figure 38A). The obtained hierarchical zeolites showed
excellent catalytic properties in the Beckmann rearrangement
of cyclohexanone oxime to ε-caprolactam (Nylon-6), but their
microporous counterparts showed lower catalytic activities and
shortened lifetimes. The comparison shown in Figure 38B
indicates that the conversion of the cyclic oxime over the
microporous SAPO-34 significantly decreased (90% to about
40%) as the oxime size increased, while HP SAPO-34 retained
almost 100% conversion, in spite of the cyclic oxime size.
Similar results were also observed with hierarchical Beta
zeolite, formed by the aggregates of nanozeolites with an
additional mesoporosity.584 Besides, hierarchically porous
Silicalite-1, which contained Silicalite-1 nanocrystals and
mesopores (5−20 nm), exhibited a high catalytic performance
in the Beckmann rearrangement of cyclohexanone oxime to εε-
caprolactam.586 Under the same reaction conditions, hierarchi-
cally porous Silicalite-1 exhibited both higher conversion of
cyclohexanone oxime (97% vs 60%) and higher selectivity
(92% vs 42%) of ε-caprolactam as compared to conventional
Silicalite-1. The high catalytic activity was attributed to the
presence of hierarchical porosity for increasing the diffusion
rate of the reactants (cyclohexanone oxime) and products (ε-
caprolactam) in Beckmann rearrangement.586 Erigoni et al.587
further evaluated the catalytic performances of the desilicated
ZSM-5 zeolites with different Si/Al ratios in the conversion of
cyclohexanone oxime to ε-caprolactam. They found that the
hierarchical catalysts exhibited an increased selectivity toward
ε-caprolactam, compared with the microporous H-ZSM-5
zeolite. The superior catalytic performance was due to the
improved diffusion and the enhanced accessibility of acid sites
through the intracrystalline mesopores.
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Figure 38. (A) Graphical illustration of a hierarchically porous SAPO-
34 catalyst containing isolated silanol sites (a) within the mesopores
and isolated Brønsted sites (b) in the micropores. Catalytic
performance of microporous SAPO-34 and hierarchically porous
SAPO-34 (HP SAPO-34) in the vapor-phase Beckmann rearrange-
ment of (B) cyclohexanone oxime and (C) cyclooctenone oxime.
Adapted with permission from ref 585. Copyright 2015 American
Chemical Society.
In conclusion, the Beckmann rearrangement of cyclo-
hexanone oxime is a reaction that either proceeds on the
external surface of zeolites or is severely diffusion-limited, thus
benefiting from an additional larger-pore transport system in
the zeolites. The hierarchically porous zeolites show high
selectivity to ε-caprolactam along with an increased reaction
rate. The largest improvement in catalytic performances was
found in these well-connected mesopores within the micro-
porous framework which are accessible to the external surface.
4.1.3. Fischer−Tropsch Synthesis Process. The Fisch-
er−Tropsch synthesis (FTS) process is a widely used
heterogeneous catalytic process for the production of clean
hydrocarbon fuels or chemicals from syngas (CO + H2)
derived from nonpetroleum feedstocks such as natural gas,
coal, or biomass.741 Recently, the FTS process has attracted
great interest due to the global demand to reduce the
dependence on petroleum for producing fuels and chemicals.
The key challenge for FTS is the control of product
distributions, which are typically unselective and generally
follow the Anderson−Schulz−Flory (ASF) distribution.742
Numerous studies have been carried out to synthesize efficient
FTS catalysts with high C5+ selectivity.743 Co nanoparticle
(NP)-supported catalysts are widely used due to their high
selectivity toward n-paraffins, and the acidic zeolites are
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commonly used as carriers for FTS catalyst.743−746 However,
severe diffusion limits in conventional zeolites lead to high
CH4 and C2−C4 selectivities.747 Thus, hierarchically porous
zeolites are considered to be promising supports in bifunc-
tional FTS catalysts, which provide improved product
selectivity toward long-chain hydrocarbons. Besides, sintering,
which is the main cause of deactivation for cobalt-based FTS
catalysts,748,749 can be prevented by maximizing the spatial
distribution of active-phase crystallites over the support
surface.749,750 Thus, the availability of accessible surface area
is crucial when designing stable FTS catalysts. Sartipi and co-
workers593,594 reported that the large external surface areas of
hierarchically mesoporous MFI zeolites enabled the large
loading amounts of Co NPs and improved their accessibility to
reactants, thus leading to high catalytic activity in the FTS
process and low selectivity of short-chain hydrocarbons (<C4)
when compared with the microporous counterparts. Hierarchi-
cally porous ultrastable Y (USY) and Y zeolites were also used
as catalytic supports for FTS.588,589 The mesoporous H-USY
zeolites used as supporting materials for Co NPs can improve
catalytic activity.588 The increased mesopore surface areas of
the hierarchical zeolites enabled a larger loading of cobalt onto
the samples593,594 and improved their accessibility to reactant
molecules, thus ameliorating the activity and selectivity
performance of the bifunctional reactions in comparison with
their microporous counterparts.751 Peng et al.589 further
reported the advantages of mesoporosity in FTS. The Co-
supported mesoporous Y zeolites exhibited an improved
catalytic conversion as compared to Co-supported micro-
porous Y zeolites. The MCM-22 molecular sieve, a layered
zeolite with MWW structure, was constructed by layers linked
together along the c-axis by oxygen bridges and having two
independent multidimensional pore systems. Besides, its
special thin platelet morphology resulted in high external
surface area.590,591 This new micro- and mesoporous material
with controlled acid−base properties was also employed as a
support for Co NPs.752 Co/MCM-22 contained a smaller and
uniform Co nanocluster than the sample using amorphous
SiO2 as carriers (Co/SiO2). Co/MCM-22 exhibited the
highest selectivity to long-chain hydrocarbons (C5+) when
using MCM-22 supports with the appropriate Si/Al ratio. The
higher C5+ selectivity was attributed to particular properties of
the Co particles, indicating that the structure of the MCM-22
played an important role in determining and controlling the
selectivity in FTS.752 ITQ-2 and ITQ-6 zeolites were prepared
by the delamination of layered zeolite precursors with the
MWW (MCM-22) and FER (ferrierite) structure, respectively.
ITQ-6 contained a larger fraction of accessible external surface
than ITQ-2, which was due to the distinct rearrangement of
the layers in the two materials that originated from the
different structures and dimensions of the zeolitic layers in
ITQ-2 and ITQ-6. These delaminated zeolites, with a very high
external surface area of more than 600 m2 g−1, were found to
be efficient supports for dispersing active metal phases.592 For
a comparison, a mesoporous silica MCM-41 and a commercial
amorphous SiO2 were used as supports. MCM-41 had a
narrow distribution of pores in the mesopore range. The pore
diameter of MCM-41 calculated by the BJH method was
observed to be 3.1 nm while the delaminated ITQ-2 and ITQ-
6 zeolites exhibited a wide pore-size distribution ranging from
micro- to macropores. The Co-supported pure-silica ITQ-2
and ITQ-6 exhibited a much higher reducibility (88−89 wt %)
as compared to MCM-41 (38 wt %). The C5+ selectivities over
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Figure 39. STEM images of (A) 30 Co/Beta-NS and (B) 30 Co/MFINS (insets are corresponding high-magnification STEM images). (C)
Schematic illustration of Co/zeolite nanosponge participating in Fischer−Tropsch synthesis and the diffusion pathway for reactants and products.
(D) CO conversion rates in Fischer−Tropsch synthesis plotted vs the Co loading amount on Beta-NS, MFI-NS, and MCM-41. Adapted with
permission from ref 598. Copyright 2017 American Chemical Society.
the Co-supported ITQ-2 and ITQ-6 were approximately 72%,
which were much higher than those using mesoporous silica
MCM-41 (Co/MCM-41, 45 wt %) and amorphous SiO2 as
supports (Co/SiO2, 65 wt %).
Constructing a special hierarchically porous zeolite catalyst
with a core−shell structure is another effective way to increase
the selectivity toward desired products. He et al.595 developed
a hierarchically porous ZSM-5 zeolite with a core−shell
structure by coating the H-ZSM-5 membranes on the surface
of the preshaped Co/SiO2 pellets. The prepared hierarchically
porous zeolite with a core−shell structure exhibited an
improved selectivity toward light hydrocarbons and efficiently
inhibited the formation of long-chain hydrocarbons of C11+.
Besides, the catalyst was stable in a 100 h test reaction. Kim et
al.596 prepared Co NP-encapsulated mesoporous zeolite
nanosponge (Co/NS-MFI) for FTS. The zeolite support was
constructed by disordered stacking of 2.5 nm thick MFI zeolite
nanolayers, which had a narrow mesopore distribution
centered at 4 nm. The Co/NS-MFI exhibited a similar CO
conversion (11.2 vs 11.3 mmol h−1) as compared to the
conventional alumina-based catalysts (Co/γ-Al2O3). However,
the product distributions were completely different. Co/NS-
MFI showed an increased selectivity toward branched
hydrocarbons in the gasoline range (C5−C11) while Co/γ-
Al2O3 exhibited higher selectivity toward hydrocarbons in the
diesel range (C12+). The high selectivity of the Co/NS-MFI
catalyst to gasoline-range hydrocarbons was due to the highly
accessible strong Brønsted acid sites in the hierarchically
porous zeolite support.597 From the above results, it is believed
that the ultrathin zeolite frameworks and additional porosity
due to the stacking of these nanolayers offered a short diffusion
path for branched hydrocarbons.596 Similarly, Han et al.598
realized the large loading amounts of Co NPs on mesoporous
ZSM-5 (Co/MFI-NS) and Beta zeolite nanosponges (Co/
Beta-NS), resulting in Co nanowires or networks that filled
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throughout the mesoporous channels (Figure 39A−C). The
catalytic conversion rate of these samples was measured in the
FTS reaction. For a comparison, an ordered amorphous
mesoporous aluminosilicate (MCM-41) was used to support
the same amount of Co. Figure 39D indicates the FTS catalytic
performance depending on the Co loading on the catalysts.
This result showed that the Co/NS-zeolites achieved much
higher CO conversion rates as compared with the Co/MCM
with the same Co loading. The excellent catalytic activities of
these supported mesoporous zeolite nanosponges indicated
that a large portion of the surfaces was accessible for high
catalytic activity through the zeolitic micropore apertures
located on the mesopore wall.598
In conclusion, the FTS is a structure-sensitive reaction
exhibiting maximum catalytic activity when the cobalt particle
diameter is in the range 4−6 nm. Hierarchically ordered
porous zeolites having a high surface area and a narrow pore-
size distribution have been used as supports for preparing Co-
based FTS catalysts with the aim of improving Co dispersion
and controlling the product distributions by confining the
cobalt particles inside the mesopores. The introduced meso- or
macropores in the hierarchically porous zeolites also improved
their accessibility to reactant molecules, benefiting the activity
and selectivity of the FTS reactions compared to their purely
microporous counterparts. Thus, hierarchically porous zeolites
with large surface areas, ordered and uniform mesopores, and
abundant meso- or macropores are desired catalysts for FTS
synthesis.
4.1.4. Hydroconversion Process. The hydroconversion
processes, including hydrocracking (HDC), hydroisomeriza-
tion (HDI), and hydrodesulfurization (HDS), require bifunc-
tional catalysts containing both acidic and metal functions. The
balance between these two functions plays a key role in the
design of novel hydroconversion catalysts. Nanozeolites and
hierarchically porous zeolites have been widely used as
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Figure 40. (A−C) Morphology and catalytic properties of the hydrocracking of n-hexadecane over Pt/MZAT0.2-PI0.02@MSA: (A) SEM images
of pristine MZAT0.2-PI0.02@MSA with insets showing the schematic of the core−shell composite comprising a mesoporous ZSM-5 core and an
Al-containing mesoporous silica shell together with HRTEM images of Pt/MZAT0.2-PI0.02@MSA and the size distribution of Pt particles; (B)
conversion of n-hexadecane vs time on stream; and (C) the selectivity of C5−C11 vs conversion over Pt/ZSM-5 and Pt/MZAT0.2-PI0.02@MSA.
Adapted with permission from ref 601. Copyright 2014 The Royal Society of Chemistry. (D, E) Morphology and catalytic properties of the
hydrodesulfurization of refractory 4,6-dimethyldibenzothiophene over CoMoS2/NTS-1: (D) SEM images of the NTS-1 sample with the inset of
TEM images of CoMoS2/NTS-1; (E) dependence of the 4,6-DMDBT conversion on reaction time over various catalysts. Adapted with permission
from ref 611. Copyright 2017 Elsevier. (F, G, H) Morphology and catalytic properties of the hydroisomerization of n-dodecane over hierarchical
Pt/SAPO-11 catalysts: (F) SEM images of SAPO-11-H1 with insets of schematic of the hierarchical SAPO-11 together with HRTEM images and
corresponding electron diffraction; (G) conversion of n-dodecane vs temperature; and (H) the selectivity to isomers vs conversion over Pt/SAPO-
11 catalysts of C5−C11 vs conversion over Pt/ZSM-5. Adapted with permission from ref 600. Copyright 2017 The Royal Society of Chemistry.

supports due to their appropriate acidic properties, improved
molecular transport properties, and high metal dispersion.
4.1.4.1. Hydrocracking Process. Unlike fluid catalytic
cracking (FCC) which produces gasoline from heavier oil
fractions based on a monofunctional acidic catalyst, hydro-
cracking (HDC) produces high-value middle-distillates (diesel
and kerosene) and base oils from the upgrading of vacuum gas
oil (VGO), light cycle oil (LCO), and demetallized oil (DMO)
fractions by a hydrogen-addition process using a bifunctional
(acidic and metallic) catalyst.753 HDC catalysts are bifunc-
tional catalysts with both hydrogenation and acid functions, in
which the acidic components assist in the cracking and
isomerization activities while the supported metals assist in
hydrogenation activity.754
Currently, many efforts are made to develop new types of
catalysts based on hierarchical zeolites in the HDC
reaction.672,755,756 Introducing mesopores into the zeolites or
AW
reducing the zeolite crystalline size can efficiently overcome
the diffusion limitations and significantly accelerate the mass
transfer to and away from the catalytic centers, thus reducing
the possibility of secondary reactions which cause coke
formation and catalyst deactivation.757 Therefore, catalyst
supports with open hierarchical pore structures contribute to
high catalytic activity.
Hierarchical USY zeolite was prepared using commercially
available zeolite H−Y (Zeolyst, CBV760) as the original
material by steaming and acid leaching.599,307 Base leaching
and the following acid-wash were also used on H−Y, according
to the systematic studies of Groen et al.491 The resultant
hierarchical USY zeolite with an intracrystalline trimodal
porosity containing micropores (ca. 1 nm, from the zeolite),
smaller spongelike mesopores (ca. 3 nm, from base
desilication), and large mesopores (ca. 30 nm, from steaming
and acid leaching) was used as a cosupport with alumina for
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the NiMoS2 catalyst in the HDC of VGO.324 The trimodal
porosities in the hierarchical USY zeolite crystals were
interconnected in a single zeolite crystal. Owing to the rapid
mass transfer of hydrocracking products from the micropores,
the secondary cracking was thus almost fully suppressed.8 The
Pt/hierarchical USY zeolite showed high selectivity toward
higher-boiling-point fractions and exhibited extremely low
coke formation. Besides, the coke formation over the Pt/
hierarchical USY zeolite was significantly reduced as compared
to that in the commercial catalyst, indicating a higher catalyst
stability which is a direct benefit of its enhanced porosity.
Hierarchically porous zeolite with various morphologies,
such as core−shell and fibers, were reported.601,604 For
example, hierarchically core−shell structured ZSM-5 compo-
site, containing an ordered mesoporous aluminosilicate shell
and a mesoporous ZSM-5 core, was obtained by a one-pot
two-step treatment including a controlled desilication in
NaOH solution and a self-assembly with the help of a triblock
copolymer.601 The obtained sample contained interconnected
mesopores and a gradient acidity distribution from shell to
core. Further incorporation of Pt nanoparticles into the
mesoporous shell resulted in a highly efficient catalyst for the
n-hexadecane hydrocracking (Figure 40A). The catalysts
achieved a higher n-hexadecane conversion and a higher C5−
C11 selectivity than those of Pt/ZSM-5 in the whole reaction
time (Figure 40B,C).601 Hierarchical structured fibers
constructed by NiO−WO3 and Y zeolite nanocrystals were
also used as catalysts for n-heptane hydrocracking.604 The
hierarchically porous zeolite composite fibers showed a high
conversion of 98.81 wt % and a low coke amount of 0.40 wt %
at 350 °C. Such a superior performance was attributed to the
enhanced accessibility due to the nonwoven mesh/network of
catalytic hierarchically porous fibers which prevent the
agglomeration of the zeolite nanoparticles. The nanosized
nature of zeolite, the shape of the fibrous catalyst, and the
mesoporous character of the hierarchically porous zeolite
composite fibers accelerated diffusion and improved accessi-
bility of the reactants to the catalyst active sites as proven by
the high total n-heptane conversion and high hexane and
isohexane selectivity in n-heptane hydrocracking.
In conclusion, the hydrocracking process is achieved by the
initial upgradation of polyaromatics which requires catalysts
with efficient catalytic performances and low deactivation and
the second hydrocracking process of high-molecular-weight
hydrocarbons using a bifunctional and hierarchically porous
catalyst (i.e., catalyst possessing both acid and metal
functions). Therefore, one of the most important factors in
the hydrocracking process is the choice of catalyst. Hierarchi-
cally porous zeolites with highly interconnected pores and
strong zeolite characters are proven to be highly desirable.
4.1.4.2. Hydroisomerization Process. The hydroisomeriza-
tion process of linear alkanes (n-alkanes) is a key refinery
process to transform petroleum fractions into high-octane
gasoline. n-Heptane is usually used as a model reactant for
fundamental research.758 The catalysts used for hydro-
isomerization reactions usually contain two components, i.e.,
noble metals for hydrogenation and acid sites for skeletal
isomerization. However, no catalysts have been practically used
for the hydroisomerization process of longer-chain alkanes
(C7−C8). According to the kinetic studies undertaken on the
hydroisomerization of C5−C7 alkanes over platinum-contain-
ing mordenite, the reaction rate for C5−C6 alkanes was
primarily constrained by the isomerization process on acid sites
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while, for n-alkanes (n > 6), it was mainly limited by
diffusion.759 The introduction of mesopores into the catalyst
support can efficiently solve the problem. For example, a
hexagonal structured mesoporous SAPO-5 was prepared by
assembly of SAPO-5 building units and used as the catalyst
support for the hydroisomerization of the long-chain hydro-
carbon (1-octene).760 The resulting mesoporous SAPO-5-
based catalysts exhibited excellent branched isomer selectivity
(25−30%) compared to SAPO-5-based catalysts, which
showed relatively low selectivity toward branched isomers
(5%). Besides, the mesoporous SAPO-5 yielded higher 1-
octene conversion (∼85% 1-octene) than most of the reported
microporous SAPO-n. Liu et al.761 synthesized Beta-MCM-41
composites combining the advantages of both the micropores
from microporous zeolite Beta and the mesopores from the
MCM-41. The catalysts were used as porous supports and
showed excellent catalytic performance in the hydroisomeriza-
tion of n-heptane. Furthermore, the effects of the micro-
mesoporous structure with dealuminated mesopores in the
hydroisomerization of n-heptane were investigated.762 Tao et
al.600 prepared a series of hierarchical SAPO-11 zeolites
(samples SAPO-11-H1 to SAPO-11-H12) via the dry-gel
conversion of a silicoaluminophosphate−organosilane compo-
site with different compositions. For SAPO-11-H1, it was
assembled by nanosheets with thicknesses of 50 nm, which
were in turn aggregated by SAPO-11 nanocrystals with sizes of
10−50 nm (Figure 40F). The resultant hierarchical SAPO-11
zeolite microspheres had uniform intercrystalline mesoporosity
(ca. 4.3 nm). After loading Pt nanoparticles, the catalysts were
evaluated in the hydroisomerization of n-dodecane and showed
much higher isomerization selectivity than the catalysts that
used conventional SAPO-11 as supports (Pt/SAPO-11-C) at
the same conversion, indicating that the introduced mesopores
in the zeolites can significantly boost their catalytic perform-
ances (Figure 40G,H). Kim et al.763 prepared hierarchically
porous SAPO-11 with carbon templating (C2-SAPO-11). The
carbon-templated SAPO-11 catalysts showed remarkably
enhanced isomerization yields (84%) compared with Pt/
SAPO-11 (44%). Thus, it was concluded that the introduction
of secondary mesoporosity is beneficial for hydroisomerization.
Hierarchically porous BEA zeolite aggregated by nanocrystals
was also used as cosupports for the n-hexadecane hydro-
isomerization reaction.764 The composite catalysts showed a
catalytic activity 3.5 times greater than that of the purely
microporous zeolite. Besides, the yield of isomers increased
from 35 to 80 wt %.
In conclusion, the hydroisomerization reactions required
bifunctional catalysts containing both the noble metals for
(de)hydrogenation and the acid sites such as zeolites for
skeletal isomerization. However, the narrow micropores in
conventional zeolites usually cause severe diffusion limitation
on the reactants and products. Therefore, it is of significant
importance to shorten the diffusion length and expose more
available acid sites. Integrating additional pores into micro-
porous zeolites is an effective strategy to overcome the
inherent diffusion limitations and improve the utilization of
zeolites.
4.1.4.3. Hydrodesulfurization Process. To comply with
strict environmental regulations, the complete removal of
highly refractory molecules such as 4,6-dimethyldibenzothio-
phene (4,6-DM-DBT) from petroleum feedstock and
especially from inferior diesel is highly required. The
hydrodesulfurization (HDS) process is one of the most
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effective methods to convert the organic sulfur compounds
into hydrogen sulfides.603 The hydrocracking and hydro-
isomerization processes summarized above usually involve
hydrogenation of sulfur-containing substances. In order to
better distinguish the hydrotreating process of sulfur-
containing substances and non-sulfur-containing substances,
the hydrodesulfurization process is reviewed separately in this
section. It is confirmed that noble-metal-supported catalysts
have a much better hydrogenation performance than conven-
tional metal sulfides in HDS.602 γ-Al2O3 is the widely used
commercial HDS catalyst support due to its low cost, large
surface area, high stability, and excellent formability.606
However, these commercial HDS catalysts produce diesels
that hardly meet the strict specifications of diesel quality from
increasingly lower-quality raw diesels.765 Thus, novel HDS
catalysts with high catalytic efficiency are desired. Both the
active centers and the supports play an important role in the
catalytic performance of catalysts. The pore structures of
support materials are considered as the most important factors
in deciding the final catalytic performance of the related HDS
catalysts.605 Zeolites have large surface areas that facilitate
metal dispersion and unique zeolite frameworks that enable
strong metal−support interactions.766 Moreover, the active
metal clusters can be confined in the microporous zeolite
channels. As discussed above, the further introduction of
mesopores or macropores into microporous zeolites could
significantly accelerate the mass transfer of the reactants and
products to and from the active sites, thus making them ideal
support or cosupport materials for HDS.607
Sun et al.767 were the first to report that the mesoporous Na-
ZSM-5-supported Pt catalysts (Pd/MNZ-5) exhibited a much
higher HDS conversion (86% vs 3%) than the catalysts that
used conventional Na-ZSM-5 as supports (Pd/NZ-5). The
sulfur removal by Pd/MNZ-5 was 29 times higher than for Pd/
NZ-5. The bulky 4,6-DM-DBT molecule cannot enter the
small micropores in MNZ-5; thus, they can only react on the
outer surface of the zeolites and cannot reach many active
centers. These results indicated that MNZ-5 with mesopores
was a better catalyst support in the HDS of 4,6-DM-DBT than
NZ-5 without mesopores, thus proving that mesoporosity in
the supports played a positive role in sulfur removal. The
catalytic performance of Pd-supported mesoporous Y, Beta,
and ZSM-5 in the HDS was studied.768 Mesoporous zeolite Y
was prepared by using N,N-dimethyl-N-octadecyl-N-(3-trie-
thoxysilylpropyl) ammonium [(C 2 H 5 O) 3 SiC 3 H 6 N-
(CH3)2C18H37]+ as a mesopore template. After loading Pd
on the mesoporous zeolite HY, the catalyst showed a higher
catalytic performance in the HDS of 4,6-DM-DBT. Compared
with Pd-supported mesoporous zeolites Beta and ZSM-5
(80.0% and 73.4% for Pd/HBeta-M and Pd/HZSM-5-M,
respectively), Pd/HY-M showed an improved catalytic
performance in HDS of 4,6-DM-DBT (97.3%). The higher
activity of Pd/HY-M than those of Pd/HBeta-M and Pd/
HZSM-5-M was ascribed to the introduced mesoporosity and
the larger micropores of zeolite Y than those of zeolite Beta
and ZSM-5. Besides, both theory and experiment confirmed
that 4,6-DM-DBT was too large to enter the internal
micropores of zeolites ZSM-5 and Beta, but the micropores
within zeolite Y are more accessible due to the additional
interconnected mesoporosity.768 Hierarchically porous mor-
denite made by crystalline nanosheet assemblies (NS-HMOR)
with a large external surface area and intercrystalline
mesoporous structure was also prepared as a support material
AY
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in HDS catalysts.608 After the dispersion of nickel and
phosphorus species onto NS-HMOR, the obtained Ni2P/NS-
HMOR catalyst exhibited a higher HDS activity (TOF = 1.9 ×
10−3 s−1) and better stability in 4,6-DM-DBT HDS than a
porous SiO2-supported Ni2P catalyst. The large amount of
accessible acidic hydroxyl groups on the NS-HMOR surface
facilitated the formation of small Ni2P clusters on the external
surface. Besides, the open micropores at the NS-HMOR
surface helped to prevent their aggregation. Zhang et al.611
prepared hierarchically porous zeolite TS-1 with crystalline
nanorods (NTS-1) (Figure 40D) having a large accessible
surface area. Following the introduction of Co and Mo species
and sulfidation, the obtained catalyst (CoMoS2/NTS-1)
showed a higher catalytic activity in the HDS of 4,6-DM-
DBT than the γ-Al2O3 and binary SiO2−TiO2-supported
catalysts (Figure 40E).
Generally, zeolite nanocrystals were mixed with mesoporous
alumina to form the zeolite−alumina cosupport for HDS
catalyst. The micro-mesoporous composite materials aim at
combining the advantage of microporous and mesoporous
materials and overcoming the disadvantages of both the weak
acidity in the mesoporous zeolites and the diffusion limits in
the microporous zeolites. For example, the as-synthesized
ZSM-5 zeolite nanocrystals were enwrapped by mesoporous
KIT-6 materials to form a composite support for HDS
catalyst.609 The mesoporous KIT-6 material was reported to
possess a large pore diameter of ∼8 nm610 and complementary
pores between the two main channel systems,612 which could
enhance the accessibility of the active sites. The ZSM-5/KIT-
6-supported NiMo sulfides showed a 4,6-DMDBT conversion
double that of a conventional NiMo/Al2O3 catalyst under the
same reaction conditions. Except the pore size, the
morphology and mesochannel in the supports also had a
great effect on the catalytic performance. Gao et al.613
synthesized mesoporous Beta-SBA-15 zeolites with different
morphologies, such as platelet (BS-PL), sphere (BS-SP), short-
rod (BS-SR), and long-rod (BS-LR), and used them as catalyst
supports for the HDS of FCC gasoline. The platelet BS-PL
exhibited large pores and short mesochannels that accelerated
the mass diffusion. The sphere BS-SP showed higher mesopore
volumes that facilitate the bulky reactants to and away from the
active sites. However, the short-rod BS-SR and long-rod BS-LR
had long mesochannels and fewer mesopore cavities, resulting
in a poor diffusion ability. The catalytic results confirmed that
the platelet CoMo/Beta-SBA-15 exhibited the highest HDS
conversion (97.6 wt %). Such an excellent HDS ability was
attributed to the special morphology and appropriate
mesochannels of the catalysts.
In conclusion, the hydrodesulfurization of thiophene and its
derivatives in the crude oils is an important process for first-
stage desulfurization in the refinery industry owing to its high
activity, recyclable, and stability together with large sulfur
tolerance. Generally, HDS catalysts are synthesized by
dispersing active phases on a support. The support, providing
high surface area to maximize active phase dispersion and
strong acidic sites to give additional reactivity, is decisive for its
final catalytic performance. The mesopores and/or the
macropores of the catalysts are crucial factors for the
dispersion of active metal species and the diffusion of the
reactants and the products. Therefore, hierarchically porous
zeolite-based supports with interconnected meso- or macro-
pores, large surface area, strong acidity, and high hydro-
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Figure 41. (A) Three structure-directing agents used for the synthesis of bulk Fe/ZSM-5 zeolite (tetrapropylammonium hydroxide, TPAOH) and
Fe/ZSM-5 zeolite nanosheets [Fe/ZSM-5(4N,360)-st (C22−6−6−6−3 Br4) and Fe/ZSM-5(2N,360)-st (C22−6−3 Br2)]. (B) Illustration of the
oxidation of benzene to phenol. (C) Catalytic properties of Fe/ZSM-5 zeolite catalysts in the oxidation of benzene to phenol and corresponding
TEM images. Adapted with permission from ref 617. Copyright 2017 American Chemical Society.

thermal/chemical stability are desired catalysts for the HDS
reaction.
4.1.5. Oxidation Reaction. 4.1.5.1. Direct Oxidation of
Benzene to Phenol. Phenol and its derivatives are important
raw materials for drugs, insecticides, and dyes in indus-
try.769,770 Currently, the dominant industrial route to produce
phenol is the environmentally unfriendly partial oxidation of
cumene. An alternative process is the direct oxidation of
benzene to phenol (BTOP) with nitrous oxide. Almost 100%
selectivity toward phenol was reported over Fe-ZSM-5 zeolites
in this reaction.614 However, the sole and relatively small
micropores in ZSM-5 zeolite cause poor diffusivity of benzene
and phenol, leading to the heavy coke deposition on the
micropores and fast deactivation. An efficient solution is to
introduce secondary pores into zeolites. Mesoporous Fe-ZSM-
5 zeolites were prepared by a hydrothermal process and a
subsequent desilication treatment. The resultant zeolites
exhibited an improved catalytic performance and increased
stability in the BTOP reaction due to the decreased diffusion
path and increased accessibility to the active sites.615 Shahid et
al.616 further subjected the purely microporous ZSM-5 zeolite
(HM27) to alkali treatment (HM27_AT) and a combination
of post-treatment sequences by steam-acid-alkali treatments
(HM27_St_AcT_AT). The SBET and Vmeso of HM27,
HM27_AT, and HM27_St_AcT_AT increased from 414 m2
g−1 and 0.10 cm3 g−1, to 434 m2 g−1 and 0.21 cm3 g−1, and to
489 m2 g−1 and 0.49 cm3 g−1. The catalytic performances of
these three samples (HM27, HM27_AT, and HM27_St_Ac-
T_AT) were tested in the direct oxidation of benzene to
phenol. The HM27_St_AcT_AT sample exhibited not only
the highest initial benzene conversion but also a high catalyst
stability with time on stream. After 3 h of reaction, the benzene
conversion of HM27_St_AcT_AT, HM27_AT, and HM27
decreased from 40% to 24%, 35% to 13%, and 29% to 6%,
respectively. The decrease rates in the phenol selectivity of the
AZ
HM27_St_AcT_AT, HM27_AT, and HM27 sample at 480
°C are 9%, 78%, and 99% of its initial value, respectively. The
results indicated that dealumination (steam treatment followed
by acid treatment) can boost the catalytic performance more
effectively than desilication (alkali treatment) in the BTOP
reaction. The hierarchical Fe-ZSM-5 zeolite catalysts, which
were directly synthesized by adding an amphiphilic organo-
silane618,619 and a diquaternary ammonium surfactant617,620
into a Fe-ZSM-5 synthesis gel, were reported to exhibit much
lower deactivation rates compared to conventional Fe-ZSM-5.
For example, Koekkoek et al.620 synthesized hierarchically
porous Fe/ZSM-5 zeolite for the first time by the stacking of
nanosheets using diquaternary ammonium structure-directing
agents [SDAs, [C 22H 45 −N + (CH 3) 2 −C 6 H12 −N + (CH3 ) 2 −
C6H12−N+(CH3)2−C6H12−N+(CH3)2−C3H7−Br4,
C 2 2 − 6 − 6 − 6 − 3 ·Br 4 ] and [C 2 2 H 4 5 −N + (CH 3 ) 2 −C 6 H 1 2 −
N+(CH3)2−C3H7−Br2, C22−6−3·Br2], Figure 41A]. The small
size along the b-direction in zeolite nanosheets significantly
shortened the intracrystalline pathways, thus reducing the mass
transfer limitations caused by the long diffusion paths in the
micropores that the reactants and products of similar size had
to travel.617 The hierarchically porous zeolites synthesized by
C22−6−6−6−3·Br4 (Fe/ZSM-5(4N,360)-st) and C22−6−3·Br2 (Fe/
ZSM-5(2N,360)-st) were made by the stacking of nanosheets
with a thickness of ∼6−8 and 3 nm. Fe/ZSM-5(2N,360)-st
produced a higher phenol yield (185.2 mmol g−1 after a 24 h
reaction) in the selective oxidation of benzene to phenol than
both Fe/ZSM-5(4N,360)-st (145.1 mmol g−1 after a 24 h
reaction) and bulk zeolites Fe/ZSM-5(TPA,360)-st (85.8
mmol g−1 after a 24 h reaction, Figure 41B,C).617 Moreover,
the zeolite nanosheets retained more than half of their initial
activity after 24 h. The improved catalytic stability was due to
the shorter diffusion pathways of coke or coke precursors to
the external surface of the hierarchically porous zeolite
nanosheets. The carbonaceous coke was mostly deposited in
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the mesopores. In contrast, diffusion paths to the external
surface of bulk zeolite were much longer. The cokes mostly
deposited in the micropores. Besides, the formation of coke
was largely reduced in the hierarchically porous zeolites made
by the stacking of zeolite nanosheets because of the short
molecular traffic distances in the zeolite nanosheets. The
carbonaceous byproducts were mainly deposited in the
mesopores between the nanosheets rather than in the
micropores. Contrarily, it was found that the micropore
volume in the bulk Fe/ZSM-5 decreased greatly due to the
rapid blockage of micropores. Moreover, the secondary
reactions were effectively suppressed due to the small length
of the zeolite nanosheets in the direction of the straight
channels.620 Hierarchical Fe/ZSM-5 zeolites made of nano-
sheets were also prepared from a typical synthesis gel for Fe/
ZSM-5, in which the conventional structure-directing agent
TPAOH was replaced by a silane coupling agent comprising a
polar head group with two quaternary ammonium centers and
a hydrophobic tail.621 The resultant hierarchical zeolite had a
similar thin sheet morphology as the zeolites reported by the
Ryoo group.157,158 Their crystallinity was equally high as the
crystallinity of bulk Fe/ZSM-5 except that the coherent length
of the crystals in the b-direction was limited for the sheetlike
zeolites. The samples exhibited improved activity and
enhanced stability in the BTOP, realizing more than 20 wt
% in benzene conversion as compared to conventional ones.621
4.1.5.2. Oxidation Reactions with Peroxides. Titanosili-
cates are highly active and environmentally friendly catalysts
used in a series of industrially important organic oxidation
reactions using peroxide as an oxidant, such as the epoxidation
of linear alkenes237,622,625−628 and cyclic olefins,177,771−776 the
oxidative desulfurization,200,629−633,777−787 the hydroxylation
of phenol,467,634,635,788−792 and the ammoxidation of cyclo-
hexanone.194,636−641,793−795 The most common titanosilicate
zeolites are titanium Silicalite-1 (TS-1).796,797 However, they
are limited in catalytic oxidation reactions of the substrates
with relatively small molecular sizes due to the medium pores
of the 10-membered ring (about 0.5−0.6 nm pore diameter).
The relatively narrow micropores in the TS-1 zeolite limit the
diffusion of reactants and products. Thus, the bulky reactants
cannot enter into the micropores and diffuse to active sites.790
The generated larger product molecules cannot diffuse out of
the micropores quickly and further convert to undesired
byproducts, leading to pore blocking and coke formation.798
The catalytic applications of titanosilicate zeolites are greatly
broadened when the diffusion path length is reduced. To
overcome the problems arising from the microporous structure
of zeolites, meso- and/or macropores are introduced by either
in situ or postsynthesis approaches.15
4.1.5.2.1. Epoxidation of Linear Alkenes and Cyclic
Olefins. 1-Hexene and 1-octene are small linear alkenes
without sterically requirements. Wu et al. introduced titanium
atoms into the MWW framework using hexamethylene imine
or piperidine as structure-directing agents.622−624 The
titanosilicate MWW (Ti-MWW) is a medium pore zeolite
with a two-dimensional system of 10-ring pores and 7.1 × 18.1
Å supercages.590 Moreover, the MWW-type lamellar precursor
converted into a micro-mesoporous hybrid346 or formed an
assembly of ultrathin nanosheets by delamination,342 both
having active sites highly accessible to the bulky molecules.
Thus, the Ti-MWW zeolite produced a conversion of 44.8 wt
% in the 1-hexene epoxidation while the conversion over the
TS-1 was only 5.8 wt %.622 Similarly, Kim et al.625 prepared
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hierarchical Ti-MCM-36 formed by pillared MWW catalyst
which exhibited a turnover number (TON) 3 times higher
than that of conventional TS-1 in 1-hexene epoxidation. In 1-
octene epoxidation, similar results for 1-hexene were
obtained.626,627 Conventional TS-1 catalysts provided a similar
conversion (2.5 wt %)626 while Ti-MWW catalysts with a
hierarchical structure once again exhibited the highest yield of
cyclooctene oxide.627 Furthermore, hierarchical TS-1 zeolite
nanocrystals were obtained by the crystallization of silanized
seeds.628 The resultant catalysts exhibited a higher catalytic
conversion than their microporous counterparts in the 1-
octene epoxidation with TBHP and showed very high oxidant
efficiencies and extremely stable 100% epoxide selectivity. .628
Moreover, hierarchically porous zeolite catalysts are mostly
applied in the epoxidation of sterically demanding molecules.
The oxidation of bulky molecule 2,4,6-trimethylstyrene is often
used as a probe reaction to study the sterical effect. Chen et
al.237 prepared a novel hierarchically micro-meso-macroporous
zeolitic TS-1 architecture using a glycerol-assisted quasi-solid-
state crystallization process described in section 2.235,242,243 All
pores of over three length scales were incorporated throughout
the final solid body to construct a highly interconnected
network of well-defined macrochannels with uniform meso-
porosity and zeolitic microchannels. The introduced meso-
pores or macropores were directly accessible from the outer
surface of the zeolite crystal and effectively enhanced the
molecular transport to/from the active sites. Such full
interconnectivity between the various levels of pores in the
resultant hierarchical zeolites maximized the benefits of
hierarchy in catalytic reactions, thus leading to superior
catalytic performances in the oxidation of 2,4,6-trimethylstyr-
ene with a conversion 17 times higher than that of their
microporous analogues. Contrarily, the introduced mesopores/
macropores are transport-wise ineffective if they are not
accessible to the outer surface of the zeolites.
The molecular dimension of cyclohexane is around 5.0 Å,
being comparable with the micropore size of medium pore TS-
1 zeolites. These molecules suffer from severe diffusion
limitations in the 10-membered-ring micropores when
compared with 1-hexene.771 Hierarchical TS-1 with highly
connected mesoporous channels was successfully synthesized
using poly(vinyl alcohol)-modified carbon nanotubes as hard
templates.772 The catalyst exhibited a much higher catalytic
activity than the conventional TS-1 in the epoxidation of
cyclohexene. The greatly improved catalytic performance was
attributed to the abundant wormlike and fully interconnected
mesopores, which made the active sites in the TS-1 zeolite
more accessible to the bulky molecules. Furthermore, alkaline
treatment of TS-1 also resulted in the formation of hierarchical
structures. The well-developed intracrystalline mesoporosity
together with the isolated Ti atoms in the tetrahedral
framework achieved a cyclohexene conversion 7-fold higher
than that of the conventional untreated microporous TS-1
while the selectivity toward epoxide reached as high as 96%.
Hierarchically structured Ti-ECNU-7P (Ti-MWW) nano-
sheets were prepared using boron to assist crystallization and
cetyltrimethylammonium bromide (CTAB) to swell and pillar
interlayers.773 The resultant Ti-ECNU-7P contained 2.5 nm
thickness zeolite nanosheets with stacked interlamellar
mesopores. Besides, such large interlayer spacing cannot be
obtained by the conventional hydrothermal method. Due to
more accessible active sites on the external surface, hierarchical
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Ti-ECNU-7 zeolites showed a much higher cyclohexene
conversion (29.8 wt %) than Ti-MWW (7.2 wt %).
Cyclooctene is another widely used bulky model substrate to
study the steric effect. The cyclooctene molecules cannot enter
the micropores of zeolites, and therefore, their further
epoxidation can only take place on the external surface of
the zeolites. The hierarchically porous titanosilicates with a
lamellar structure possessed the active Ti sites on the external
surface of the crystalline layers, which are accessible without
diffusion restrictions of the micropore system. Their
superiority over the conventional TS-1 was noticeable. For
example, a hierarchically porous titanosilicate with Si/Ti molar
ratio of 30 made by the UTL layers [Ti-IPC1-PITi (30)] was
prepared.774 The resultant Ti-IPC1-PITi (30) had a much
higher SBET and Vtot (910 m2 g−1 and 0.46 cm3 g−1 vs 339 m2
g−1 and 0.19 cm3 g−1) than the conventional large-pore Ti-BEA
catalyst, thus leading to a cyclooctene conversion (35.8% vs
14.0%) much higher than that of Ti-BEA.774 Hierarchically
porous Del-Ti-MWW with a layered structure prepared by
delaminating the Ti-MWW precursor was found to have an
enlarged accessible surface area, thus leading to a greatly
improved catalytic performance for the epoxidation of
cyclooctene.775 Furthermore, hierarchical Ti-Beta zeolite,
prepared by simultaneous desilication and titanation, exhibited
intracrystalline mesopores and outperformed its microporous
counterpart in the liquid-phase epoxidation of cyclooctene.776
The epoxide yield achieved with the hierarchical sample was
nearly 3 times higher than that with the microporous sample.
The superior catalytic performance of hierarchical Ti-Beta was
assigned to the presence of larger transport pores and the
significantly higher accessibility of the active Ti sites.
4.1.5.2.2. Oxidative Desulfurization. The oxidative desul-
furization (ODS) reaction of sulfides to sulfoxides or sulfones
can be undertaken under mild conditions, which is an effective
method to produce fuels with very low sulfur content and
considered to be the most promising process to replace the
hydrodesulfurization (HDS) process.777,778 Titanosilicates as
catalysts were mostly studied.779,780 However, their intrinsic
small micropores impose serious diffusion constraints on bulky
sulfides such as dibenzothiophene (DBT) and alkylated-DBT
such as 4,6-dimethyldibenzothiophene (4,6-DMDBT).781 Ear-
lier studies reported that TS-1 was almost inactive for the
epoxidation of the aromatic thiophene molecule and had no
catalytic activity toward DBT and 4,6-DMDBT.200 The
development of hierarchical titanosilicates can overcome the
constraints presented by solely microporous zeolites.629
Hierarchically porous TS-1 nanocrystals (HTS-1), prepared
by using commercial polymer PVA as a mesoporogen (Figure
42A), contained rich intracrystalline mesopores formed by the
stacking of nanocrystals.630 The steric hindrance of two
methyl-groups in 4,6-DMDBT seriously restrained its accessi-
bility to the active site of conventional TS-1. However, the
diffusion of 4,6-DMDBT in HTS-1 became easier because the
size of mesopores (4−20 nm) is much larger than that of 4,6-
DMDBT, leading to much higher 4,6-DMDBT conversion
than that obtained by conventional TS-1 (84% vs 18%, Figure
42B).
Hierarchical TS-1 catalyst with a smaller mesopore size (2−
3 nm) was prepared through the hydrothermal method by
using the green and cheap surfactant Triton X-100 (poly-
ethylene glycol tert-octylphenyl ether) as the mesoporous
template.631 The catalytic performances of the hierarchical TS-
1 (HTS-1) and the conventional TS-1 (CTS-1) were
BB
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Figure 42. (A, B) Morphology and catalytic properties of the
oxidative desulfurization of 4,6-dimethyldibenzothiophene (4,6-
DMDBT) over HTS-1: (A) TEM images of HTS-1 zeolite; (B)
removal rate of 4,6-DMDBT vs time over HTS-1 and CTS-1. Adapted
with permission from ref 630. Copyright 2016 Elsevier. (C, D)
Morphology and catalytic properties of the cyclohexanone ammox-
idation over hierarchical TS-1 zeolite: (C) TEM images of
hierarchical TS-1 zeolite; (D) removal rate of cyclohexanone vs
time over hierarchical TS-1 zeolite and TS-1-C. Adapted with
permission from ref 637. Copyright 2018 Elsevier.
compared in the DBT oxidation. It can be seen that the
DBT removal rate reached 100% after 3 h for HTS-1 but only
70.8% after 6 h for CTS-1. Obviously, CTS converted bulky
DBT at a relatively low rate while the HTS-1 showed a much
higher removing efficiency for DBT. It was inferred that the
catalytic activity of the catalysts increased as their mesoporous
volume and the accessible surface area increased.631 The
enhanced catalytic activity of the HTS-1 catalyst was mainly
attributed to the introduced mesopores in the zeolites. These
intracrystalline mesopores offered easy accessibility to the
active sites and accelerated the mass transport of bulky
molecules, thus facilitating the diffusion of DBT and sulfone to
the internal active sites through the mesopores and avoiding
the rapid deactivation.632 Hierarchical TS-1 zeolites with larger
intracrystalline mesopores (centered around 10 nm) were
further obtained from silanized protozeolitic units. These
nanounits were not independent and isolated units but
presented significant intergrowth, providing hierarchical TS-1
with a high thermal and mechanical stability. The hierarchical
TS-1 achieved a DBT conversion of 95% after only 30 min of
reaction and a total conversion after 1 h, much higher when
compared with the conventional TS-1 (33% DBT conversion
after 1 h). Besides, the obtained hierarchical TS-1 showed a
much higher DBT conversion than a silylated Ti-MCM-41
(11% DBT conversion after 30 min), which was related to the
crystalline nature of titanium active sites in TS-1 zeolite
compared with the amorphous Ti environment of the Ti-
MCM-41 material.799
Leng et al. prepared Ti-modified hierarchical mordenites
(Ti/MM) via an incipient wetness impregnation technique by
using tetrabutyl orthotitanate (TBOT) as the precursor of Ti
species.784 The introduced Ti species were located outside the
micropores in mordenite due to the large molecular size of
TBOT, leading to easily accessible Ti active sites over Ti/MM.
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The sulfur removal content over Ti/MM reached 98.6% after
120 min, which was nearly 4 times that of Ti-modified
conventional mordenite.784 Moreover, hierarchical Beta
prepared by the post-treatment process was reported to have
rich mesoporosity,575 and the four-coordinated Al atoms in the
framework of zeolite Beta could be easily removed by acid
treatment and replaced by other metals.785 Leng et al.633 thus
prepared Ti-containing hierarchical Beta zeolite by the
desilication−dealumination process and found that the
resultant catalyst exhibited better catalytic performances than
that obtained by direct desilication or dealumination. It was
attributed to the special post-treatment that provided catalysts
with the easier accessibility of highly active sites and richer
mesoporosity.
Generally, lamellar zeolites combine the advantages of both
the crystalline microporous structure and mesoporous
molecular sieves, providing abundant active centers with easy
accessibility. Kon et al.786 compared the catalytic performances
of the ODS reaction for various alkyl-sulfides over Ti-MWW
and interlayer-expanded Ti-IEZ-MWW. The conversion over
Ti-IEZ-MWW (64 wt %) was nearly double that for Ti-MWW
(36 wt %), confirming that enlarged porosity by the interlayer
expansion can significantly boost the diffusion performance of
the bulky diphenyl sulfide molecules in the catalyst of the ODS
reaction.
4.1.5.2.3. Hydroxylation of Phenol. Titanosilicate catalysts
can catalytically oxidize both aliphatic and aromatic hydro-
carbons to corresponding alcohols, ketones, and phenols. The
methyl or hydroxyl substituents on the aromatic rings are
beneficial for further hydroxylation. Thus, titanosilicates are
promising catalysts for the conversion of phenol hydroxylation
to hydroquinone and catechol. Besides, the phenol hydrox-
ylation is a diffusion-controlled reaction.788 As introducing
mesoporosity into microporous zeolite can greatly improve the
diffusion performances of zeolite,789 Tao et al. prepared
hierarchical TS-1 zeolite microspheres with a nanorod
oriented-assembled structure by a space-confined synthesis
method, which exhibited a large external surface and rich
mesoporosity.790 The phenol conversion on such a catalyst
(29.8 wt %) was almost 2-fold higher than that on the
conventional TS-1 (15.7 wt %), confirming that fast diffusion
to and out of micropores and the rich external acidic sites were
essential for the improved catalytic performance. Tsai et al.634
investigated the influence of crystalline size of TS-1 (micro-
meter-sized μm TS-1 and nanometer sized nm TS-1) and
different post-treating methods described in section 2 on the
hierarchical pores and the catalytic properties in phenol
hydroxylation. Tetrapropylammonium hydroxide (TPAOH)
post-treatment generated a hollow structure and increased
external surface of μm TS-1 without sacrificing micropores,
while selective Si removal by NaOH leaching resulted in
hierarchically mesoporous zeolite nanocrystals. The micro-
meter-sized μm TS-1 catalyst gave a lower conversion and
lower selectivity toward dihydroxybenzenes (DHBs) than the
nanometer-sized nm TS-1 sample. Moreover, subsequent post-
treatment by TPAOH followed by NaOH can create larger
pores than the micropores of TS-1 zeolite. A higher titanium
amount, faster mass transfer, and larger pore volumes
introduced by successive post-treatment greatly improved the
catalytic activity of TS-1.
The selective oxidation of 2,3,6-trimethylphenol (TMP) to
2,3,5-trimethyl-p-benzoquinone (TMBQ) is an important
reaction since the TMBQ is the key intermediate in producing
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vitamin E.635 Hierarchical TS-1 made by the assembly of
nanocrystals, possessing randomly arranged mesopores of 26
nm and uniform particle size of 200−300 nm, was prepared
through a one-step hydrothermal synthetic strategy by utilizing
the green and cheap ammonium-modified chitosan (N-2-
hydroxy-propyl-3-trimethylammonium chitosan chloride,
HTCC) as the mesopore porogen agent. The resultant
catalysts were used to evaluate the effects of the mesoporosity
on the catalytic performance of the 2,3,6-trimethylphenol
(TMP) oxidation reactions.791 Since the bulky 2,3,6-TMP
molecules can hardly diffuse into the micropores, the oxidation
of TMP mainly occurs on the external surface of the
microporous zeolites or in the larger mesopores of the
hierarchically porous zeolites. The TMP conversion and the
TMBQ selectivity on the conventional TS-1 were around 2.13
wt % and 59.62%, but it sharply increased to 62.22 wt % and
96.97%, respectively, on the hierarchically porous TS-1, which
was also much higher than those of Ti-SBA-15 and Ti-MCM-
41.792 Zhou et al.467 further prepared hierarchically meso-
porous TS-1 zeolite by a simple steam-assisted crystallization
method. The resultant catalyst had a high surface area and
large mesopore volume, thus providing significantly higher
catalytic activity and longer catalytic lifetime than the
conventional TS-1 in the selective oxidation of TMP to
TMBQ.
4.1.5.2.4. Ammoxidation of Cyclohexanone. The cyclo-
hexanone oxime is the key intermediate for synthesizing ε-
caprolactam, which is the monomer for Nylone-6. The TS-1-
catalyzed cyclohexanone ammoximation with NH3 and H2O2
was first reported by Enichem Corporation and is considered
environmentally friendly with a high selectivity toward
cyclohexanone oxime and water as the only side product.793
However, the relatively short catalyst lifetime of TS-1 in the
cyclohexanone ammoximation severely limits its further
application in industry. The decreased activity was due to
the severe deposition of bulky byproducts on the internal
surface.794
Post-treatments, as described in section 2, can effectively
generate hollow zeolite crystals with large external surface area
and mesopore volume, which can significantly facilitate the
mass transfer of bulky molecules inside the zeolite crystal.795
For example, hierarchically mesoporous TS-1 hollow crystals
were constructed by assembling TS-1 nanocrystalline blocks
through a hydrothermal post-treatment method.636 Compared
with the hierarchically mesoporous TS-1 crystals, the hierarchi-
cally mesoporous TS-1 hollow crystals exhibited a high
cyclohexanone conversion with oxime selectivity up to 100%.
The hollow crystalline structure contributed to high surface
areas, hierarchical meso-macroporosities, and thus excellent
catalytic performances.
The alkali treatment is widely used as an effective method to
generate mesopores. For example, hierarchical TS-1 zeolites,
prepared by the dissolution−recrystallization method, ex-
hibited abundant large mesopores on the external surface
and small voids homogeneously distributed throughout the
crystal.637 These materials showed 85 wt % conversion after 90
min of the reactions while the conventional TS-1 gave only 35
wt %. The superior catalytic activity was thus due to the
enhanced diffusion and the easy accessibility to the catalytic
active sites in the presence of open mesopores (Figure 42C,D).
Wu et al.638 demonstrated that the catalyst stability of TS-1 in
the cyclohexanone ammoximation was greatly prolonged after
the TPAOH treatment. The MFI structure was not destroyed
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while the intracrystalline mesopores were created, and the pore
diameters increased as the TPAOH concentrations increased.
The catalysts exhibited more than 98% cyclohexanone
conversions and more than 99% cyclohexanone oxime
selectivity. Similar results can be found for the triethylamine-
treated TS-1 catalysts.639 Some irregular hollow cavities were
created after the treatment by desilication. The catalyst lifetime
was significantly prolonged to 30 h, which was 10 times longer
than that of the conventional TS-1.
It was reported that Ti-MWW can efficiently catalyze the
ammoxidation of cyclohexanone, which gave both cyclo-
hexanone conversion and oxime selectivity over 99%.640
Besides, Ti-MWW showed a longer catalytic lifetime than
other titanosilicates, such as TS-1.641 However, Ti-MWW
suffered from the rapid deactivation due to the deposition of
byproducts. To overcome this, Xu et al.194 coated a
mesoporous silica shell over zeolite crystallites by the sol−gel
self-assembling route. The mesoporous silica shell in the novel
Ti-MWW@mesoporous-SiO2 composite catalysts efficiently
prevented the active zeolite core from rapid coke formation,
leading to a stable duration of the catalysts.
In conclusion, the relatively narrow micropores in the
conventional zeolites usually impose a severe diffusion
limitation on the catalytic oxidation reactions of bulky
substrates. The introduction of mesopores or macropores
into microporous zeolites is an effective method for the
improvement of mass transfer and the accessibility of active
sites. The hierarchically porous zeolites with interconnected
pores that are accessible to the external surface are mostly
desired in the catalytic oxidation reactions.
4.1.6. Transformation of Methanol. Nowadays, with the
rapidly rising demand for energy and the scarcity of crude oil
resources, it becomes increasingly significant to find alternative
energy sources. Among several alternatives, the conversion of
syngas (CO + H2), produced via the gasification or reforming
process of coal,800,801 natural gas,802 or biomass,803,804 into
hydrocarbons is a potential process to provide fuels and raw
materials for petrochemicals in the future.805 The Fischer−
Tropsch synthesis (FTS) process, catalyzed by Co- or Fe-
based catalysts, is a well-known process for converting syngas
to hydrocarbons, such as diesel fuels and waxes (see section
4.1.3).742 As an alternative to the FTS process, methanol is
mass-produced from syngas and converted to a hydrocarbon.
Such a methanol to hydrocarbon (MTH) process has been
used commercially for a long time and is a key route to
produce high-value chemicals from nonpetroleum C1 sour-
ces.806 Almost all petroleum-related chemicals, especially olefin
monomers and polymers, can be produced from methanol by
this process.807 The zeolite-catalyzed MTH process exhibited
excellent product selectivity as compared with the FT
process.808 Chang and Silvestri first used zeolites to catalyze
the MTH process.809 The MTH process occurred mostly
inside the micropores of the zeolite. Thus, the medium- and
large-pore zeolites selectively led to the formation of the high-
molecular-weight aromatics and paraffins (C5−C7), while the
small-pore zeolites such as erionite (ERI), zeolite T (Linde
Type T), chabazite (CHA), and ZK-5 (KFI) formed lower
olefins (C2−C4).810,811 The MTH process was widely used to
synthesize several different classes of hydrocarbons, including
gasoline-range hydrocarbons (methanol to gasoline,
MTG),157,277,282,642,643,812−827 light olefins (methanol to
olefins, MTO),34,236,554,644−656,828−861 propylene (methanol
to propylene, MTP),90,109,657−661,862−874 or aromatics (meth-
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anol to aromatics, MTA)662−664,875−901 depending on the
catalyst and/or the process operation conditions. Besides, the
methanol dehydration leads to the formation of dimethyl ether
(methanol dehydration to dimethyl ether, MTD).665,666,902,903
4.1.6.1. Methanol-to-Gasoline-Range Hydrocarbons Proc-
ess. The zeolite-catalyzed methanol-to-gasoline-range hydro-
carbons (MTG) process, first discovered by Exxon Mobil, is
complementary to Fischer−Tropsch synthesis for the con-
version of methanol to high-octane index gasoline.812 Various
types of zeolites were tested for the production of gasoline;
among them, ZSM-5 proved to be the most promising catalyst
for the production of high-quality gasoline.813−815 The unique
interconnected micropore systems in ZMS-5 zeolites allow for
the gasoline-range hydrocarbons to diffuse out.816 However,
they suffered from the drawbacks of high coproduction of
environmentally unfriendly aromatic compounds, especially
1,2,4,5-tetramethylbenzene,817,818 and the frequent necessity
for regeneration due to their fast deactivation caused by coke
formation.819 Successive efforts were put into the development
of new MTG zeolite catalysts to suppress the formation of
aromatics. Di et al.820 synthesized a ZSM-5/MCM-48
aluminosilicate composite material by a simple two-step
crystallization process, in which the precrystallized colloidal
zeolite was added into a synthesis system of MCM-48. After
the second crystallization, the ZSM-5 phase in the composite
was interconnected with the mesostructured MCM-48 phase.
The obtained catalyst possessed a high catalytic activity,
improved selectivity toward C5−C10, and reduced formation of
aromatics and carbon depositions, which were attributed to the
enhanced mass transfer properties in the hierarchically micro-
mesoporous ZSM-5/MCM-48 composite catalysts.
The slow transportation of the reactants and products in the
relatively small micropores of the zeolite are the main causes
for the short catalyst life.277 The introduction of additional
pores can significantly boost the diffusion rate of molecules in
the zeolites, thus leading to a prolonged catalyst life.821 The
hierarchical ZSM-5 zeolite was directly prepared by hydro-
thermal treatment of a clear solution made by mixing
anhydrous sodium aluminate, tetraethyl orthosilicate, tetrapro-
pylammonium hydroxide, and deionized water without using
an additional template or zeolite seeding crystals.282 The
influence of intercrystalline mesoporosity on the catalytic
performance in the MTG reactions was carefully investigated.
The intercrystalline space referred to the network of voids
generated by the aggregation of microporous ZSM-5 nano-
crystals, which were directly accessible from the outer surface
of the zeolite aggregates. The resultant ZSM-5 with
interconnected porous hierarchy exhibited almost 100 wt %
methanol conversion and 59% selectivity toward the gasoline-
range hydrocarbons. Its coke formation was less than 2 wt %
after 24 h of reaction, while the conventional ZSM-5 zeolite
exhibited nearly 8 wt % carbon deposition. For zeolites with an
interconnected hierarchy, the mesopores in the microporous
crystals should be directly accessible from the outer surface of
the zeolite crystal to ensure that the synthesized hierarchically
porous zeolite is effective for mass transport. For example,
Fathi et al.642 studied the catalytic performance of hierarchical
ZSM-5 zeolites with intracrystalline mesopores. The presence
of intracrystalline mesopores generated by the post-treatment
of HZSM-5 catalyst using CaCO3, Na2CO3, and NaOH
solutions ameliorated the catalytic performance to produce a
higher amount of gasoline-range hydrocarbons. It is interesting
to note that the sample treated by Na2CO3 showed the most
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Figure 43. (A−C) Morphology and catalytic properties of the methanol-to-gasoline conversion over unilamellar MFI zeolite: (A) SEM image of
unilamellar MFI zeolite with a flakelike morphology. The insets are the schematic structure model for the single MFI nanosheet and TEM image of
the cross-section of the flake. Coke deposition and catalytic conversion of (B) conventional MFI zeolite and (C) unilamellar MFI zeolite in
methanol-to-gasoline conversion. Adapted with permission from ref 157. Copyright 2009 Macmillan Publishers Limited. (D, E) Morphology and
catalytic properties of the methanol-to-olefin conversion over hierarchically porous SAPO-34 catalysts: (D) SEM image of hierarchically porous
SAPO-34 with the inset of a corresponding schematic structure model; (E) methanol conversion variation with time-on-stream over conventional
microporous SAPO-34 (SM) and hierarchically porous SAPO-34 (SH2) catalysts. Adapted with permission from ref 849. Copyright 2014 The Royal
Society of Chemistry. (F, G) Morphology and catalytic properties of the methanol-to-aromatics conversion over ZSM-5 hollow spheres: (F) SEM
image of ZSM-5 hollow spheres. The insets are schematic structure model and TEM image of the cross-section of an individual nanorod crystal.
(G) Methanol conversion and time on stream over different ZSM-5 samples. Adapted with permission from ref 662. Copyright 2017 The Royal
Society of Chemistry.

appropriate acidity and greater catalytic performance among
the other treated and untreated samples in the methanol to
gasoline reactions. The yield of gasoline C5+ increased by about
43% after 4 h on stream, and the catalyst lifetime extended by
about 11.5% when compared with the conventional ZSM-5
catalyst owing to the presence of intracrystalline mesopores.
Liu et al.643 systematically explored the influence of
mesoporosity in zeolite Beta on its catalytic performance for
the MTH reaction. They found that the mesoporous Beta
showed a higher selectivity toward higher aliphatics (C4−C7)
than that of conventional Beta at both low and high
conversions ranging from 20% to 100%. This was attributed
to the hierarchically porous structure of Beta, which offered full
BE
accessibility of reactants to all catalytically active sites.
However, the conventional Beta was easily deactivated due
to the fast coke deposition on the outer surface of the catalyst
crystals, which impeded access of reactants to interior active
sites. Such a hierarchical structure reduced the resident time of
methylbenzenes in zeolite micropores and inhibited the
propagation of the aromatic-based catalytic cycle. Choi et
al.157 synthesized hierarchical MFI zeolite made of nanosheets
that were only 2 nm thick, corresponding to the b-axis
dimension of a single MFI unit cell (Figure 43A). In the MTG
conversion, the hierarchical MFI zeolites made of nanosheets
exhibited an increased catalyst lifetime and deactivated far
more slowly than the conventional MFI. The hierarchical MFI
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nanosheets exhibited a much slower coke deposition rate than
conventional MFI (45 vs 170 mg g−1 zeolite at 5 days). For the
hierarchical MFI zeolites made of nanosheets, the coke formed
mainly at the mesopore surface while, for the conventional
MFI zeolites, the coke mainly formed inside the micropores
(Figure 43B,C).822,823 The extended catalyst lifetime of the
MFI nanosheets was due to the slow deposition of coke
exclusively at external surfaces that can be attributed to the
improved mass transfer of coke precursors out of the zeolite
micropores.
4.1.6.2. Methanol to Olefin Process. Light olefins, such as
ethylene and propylene, are important raw chemicals in
industry. Light olefins are traditionally obtained by the thermal
or catalytic cracking of crude oil or by the dehydrogenation of
alkanes. The limited crude oil availability calls for an urgent
alternative technology.828 The methanol to olefin (MTO)
process is a successful nonpetrochemical route for the
production of light olefins from abundant nonoil resources
and links the nonpetroleum chemical and modern petrochem-
ical industries together.829 The MTO process, therefore,
exhibits a superior economic advantage over the conventional
naphtha cracking process and has been studied over different
types of zeolites (ZSM-5, SAPO-34, MOR, etc.).
Compared to zeolite ZSM-5, SAPO-34 with a larger pore
cavity (9.4 Å in diameter) and a smaller eight-membered-ring
micropore (3.8 Å × 3.8 Å) exhibited a much higher catalytic
performance in the MTO reaction (100 wt % methanol
conversion and over 90% selectivity to C2−C4 light olefins)
due to its unique CHA framework.830−834 However, it usually
suffers from a slow mass transport to and away from the
catalytic centers, thus increasing the possibility of secondary
reactions and finally leading to coke formation. The coke
deposition covered the active sites of the catalysts,835 resulting
in a short catalytic lifetime and low selectivity of light olefins
during the MTO reactions.836−838
Considerable efforts have been made to optimize the
diffusion performances in the SAPO-34 catalyst. Previous
studies reported that the SAPO-34 zeolites with small
crystallite size exhibited great advantages in decreasing the
coke formation rate and accelerating the mass transfer
performance.839−842 In particular, for nanosized SAPO-34s,
they exhibited an improved methanol conversion efficiency and
prolonged catalyst lifetime in the MTO conversion.843−846 The
shortened diffusion path in zeolite nanocrystals reduced the
coke formation and thus contributed to their extended catalyst
life.847 Hierarchically porous SAPO-34 was prepared as cubic
aggregates of intergrown nanocrystals using an organosilane
surfactant [3-(trimethoxysilyl)propyl]-octadecyldimethylam-
monium chloride (TPOAC) as the mesopore template
through a one-step hydrothermal synthesis (Figure 43D).849
The as-synthesized hierarchically porous SAPO-34 had a 4
times prolonged catalyst lifetime and more than 10%
improvement of light olefin (C2H4 + C3H6) selectivity in
MTO conversion than microporous zeolite SAPO-34 (Figure
43E).849 Another hierarchically ordered mesoporous zeolite
SAPO-34 (3DOm-i SAPO-34) was hydrothermally prepared
within confined ordered mesoporous carbons.851 The synthe-
sized 3DOm-i SAPO-34 showed an ordered mesoporous-
imprinted structure consisting of spherical zeolite nanocrystals
and exhibited a longer catalyst lifetime and higher selectivity
toward light olefins than conventional microporous zeolite
SAPO-34 in the MTO reaction.851
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The introduction of mesopores and/or macropores into the
microporous SAPO-34 zeolite can also significantly accelerate
the molecular transfer, reduce the coke formation, and
therefore extend the catalyst lifetime.648 Many hierarchically
micro-meso-macroporous SAPO-34 zeolites were prepared
using synthesis methods described in section 2.236,849 For
example, hierarchically porous SAPO-34 zeolites with a hollow
structure were synthesized using tetraethylammonium hydrox-
ide as the only template through a one-step nanoseed-assisted
hydrothermal synthesis.554 The as-synthesized SAPO-34
zeolites exhibited remarkably enhanced catalytic activity in
the MTO reaction with about a 4-fold extended catalyst
lifetime and more than 10% increase of the selectivity for C2H4
and C3H6 as compared to conventional microsized micro-
porous SAPO-34 zeolites. By using a similar method, they
further synthesized a series of zeolite SAPO-34 nanocrystals in
an Al2O3/H3PO4/SiO2/triethylamine (TEA)/H2O system.647
The hierarchical SH-0.3 zeolite nanocrystals (TEA/Al2O3 =
3.0) showed the highest crystallinity, abundant intracrystalline
meso-macropores, and optimized acidity, exhibiting the highest
selectivity toward ethylene and propylene (85.4%). Besides,
hierarchically micro-meso-macroporous SAPO-34 monoliths
were synthesized by the dry-gel conversion of the amorphous
silicoaluminophosphate monolith.236 The as-synthesized hier-
archical SAPO-34 had a macroporous framework constructed
by interconnected and aggregated zeolite SAPO-34 nanocryst-
als and a mesoporous structure formed by the closely stacked
zeolite SAPO-34 nanocrystals. Hierarchically structured zeolite
SAPO-34 possessed a much higher catalytic activity in MTO
reactions than that of conventional microporous zeolite SAPO-
34.236 However, it is difficult to use traditional acidic or alkali
treatment to synthesize hierarchically porous SAPO zeolites
due to their unstable frameworks.858 Liu et al.649 developed a
novel tetraethylammonium hydroxide etching post-treatment
method to obtain hierarchically porous SAPO-34 under mild
conditions. The resultant SAPO-34 was constructed by the
original micropores, mesopore (3.5 nm), and macropore (100
nm). The single-run lifetime of the hierarchical zeolites in
MTO increased without sacrificing the excellent methanol
conversion and light olefin selectivity. Chen et al.650 applied
the fluoride post-treatment route to obtain hierarchical SAPO-
34 crystals. The treatment of SAPO-34 zeolites with a fluoride
solution resulted in a preferential dissolution of the high-defect
and Si-rich interface between crystalline domains. The newly
formed mesopores were parallel to the zeolite crystalline faces.
The intersecting mesopores separated crystalline domains, thus
providing improved access to all the microporosity. The
resultant hierarchical zeolites exhibited an improved light
olefin selectivity in the MTO reaction. Besides, the fluoride
etching method can be expanded to obtain other hierarchal
SAPO-34 catalysts with improved MTO performances.651,652
A better understanding of the relationship between the
hierarchical pore structure in ZSM-5 zeolites and their catalytic
performance in the MTO reaction is crucial to design optimal
catalysts. Kim et al.644 carefully investigated the effects of
mesoporosity on catalyst activity of the MTH reaction using a
series of MFI zeolites with various mesoporosities. The reason
for catalyst longevity was the improved diffusion of coke
precursors from the micropores to the external surfaces owing
to the short pathways provided by the introduced mesopores.
They also monitored the quantity and the location of coke in
the catalyst and found that in mesoporous zeolites the coke
formed mainly on the mesopore walls while in microporous
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zeolites the coke mostly deposited inside the micropores.
Internal coke deposition caused serious deactivation of the
catalyst because it covered the acidic sites and blocked the
micropores even at a low coking level. However, external cokes
caused little hindrance to the diffusion performances unless it
covered the entire external surface of the catalyst. Meng et
al.645 used cetyltrimethylammonium (CTA) as the sole organic
template to synthesize hierarchical ZSM-5 zeolite in a one-step
approach. The introduction of additional mesoporosity
decreased the intracrystalline residence time of the inter-
mediates and extended the catalyst lifetime. The desilication
was also applied by Bleken et al. to prepare mesoporous H-
ZSM-5 zeolite catalysts.646 The catalysts showed an improved
lifetime and resistance toward deactivation in the MTO
reaction.
The interconnectivity between the additional pores and the
micropores in the hierarchical SAPO-34 zeolites determines
their final catalytic performances. Schmidt et al.34 introduced
transport pores into SAPO-34 using carbon nanoparticles and
carbon nanotubes as secondary templates as described in
section 2. The carbon nanotube-templated materials (M/T-3)
contained mesopores accessible from the outside of the
particle. However, for the mesopores created by carbon
nanoparticles (M/T-2), they were located inside the particle
and did not form a three-dimensional interconnected
mesopore network. The methanol conversion of the parent
(M/T-1) and the M/T-2 decreased after 120 min drastically
until there was no further conversion. The M/T-3 showed a
full conversion of methanol and dimethyl ether for almost 300
min time on stream. Similarly, enhanced catalytic perform-
ances were also found for hierarchically porous SAPO-34
catalysts with open mesopores.852−854 Milina and co-work-
ers855,856 further established the relationship between the
mesopore quality (i.e., the size, distribution, and connectivity
of mesopores inside the crystals) and the catalyst lifetime in
the MTO reaction. They found that the extended lifetime
resulted from the presence of open mesopores with a well-
connected intracrystalline hierarchical pore network rather
than constricted mesopores with poor connectivity. The global
connectivity of the intracrystalline pore network, therefore, is a
decisive factor in extending the lifetime of the zeolite catalysts
in the MTO reaction. Their findings emphasized the need to
appropriately tailor the hierarchically porous structure for the
optimal catalytic advantage. Sun et al.857 synthesized the
trilevel hierarchically porous SAPO-34 zeolite with an
intracrystalline micro-meso-macropore structure for the first
time. The as-synthesized catalyst exhibited a superior catalytic
performance in the MTO reaction with about a 6 times
prolonged catalyst lifetime and nearly 5% improvement in
selectivity toward ethylene and propylene compared with the
conventional microporous SAPO-34.
In addition to SAPO-34 and ZSM-5 catalysts, other zeolites
like SSZ-13,859 ZSM-22,654 ZSM-58,655 SAPO-5,654 SAPO-
11,653,656 SAPO-18,656 and SAPO-35653 were also reported in
the MTO process. Based on its unique crystalline structure,
zeolite ZSM-58 exhibits a strong shape selectivity when
compared with SAPO-34. The micropores of ZSM-58 have
narrow entrances in the range of 0.45 nm × 0.36 nm, providing
the desired shape selectivity toward short-chained olefins in the
MTO reaction. However, the increase in the diffusion
properties of reactants and products is desirable. Selzer et
al.860 synthesized hierarchical ZSM-58 zeolite via postsynthetic
desilication by sodium hydroxide and using TEA+ ions as a
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pore growth moderator. The introduced intracrystalline
mesopores exhibited a size of 3−25 nm. By increasing the
concentration of sodium hydroxide, the mesopore volume
increased up to 0.50 cm3 g−1. The desilicated ZSM-58 showed
an extended catalytic lifetime and improved product yields in
the MTO reaction as compared to conventional microporous
ZSM-58. Ahmed et al.861 adopted multistep sequential alkaline
and acid treatments to develop a more mesoporous surface
area and to offer more active sites on EU-1 zeolite. The
multistep sequential treatment was successful in creating more
mesopores as compared with the single-step treatment. The
selectivity of propylene in the MTO process was increased
from 0%, in the case of parent EU-1, to 50% together with an
enhanced catalyst stability and extended lifetime.
4.1.6.3. Methanol to Propylene Process. Propylene is an
important basic chemical for the production of polymer and
chemical intermediates, such as polypropylene, acrylonitrile,
propylene oxide, oxo alcohols, and cumene.862 Naphtha
thermal cracking and petroleum refining in fluid catalytic
cracking units are two major commercial methods for the
propylene production, and both are dependent on crude oil
resources.863 Due to the increasing demand for propylene and
rapid depletion of oil resources, new processes with high
propylene yield are needed.864 The methanol to propylene
(MTP) process is a promising alternative approach for the
production of propylene.865 Thus, it is highly desirable to
develop catalysts that can efficiently produce propylene.
To develop an ideal catalyst for the MTP reaction, stable
and high methanol conversion and propylene selectivity are
crucial.866 ZSM-5 zeolites usually exhibit low propylene
selectivity and rapid deactivation of the catalyst due to coke
formation.867 Numerous studies were undertaken to further
improve the propylene selectivity and catalyst lifetime
compared to the ZSM-5 catalyst for the MTP reac-
tion.657,658,661,868 Rownaghi et al.657 reported that the zeolite
nanocrystals exhibited a higher catalytic activity, stability, and
selectivity toward propylene compared with micronized
zeolites due to their rapid mass transfer which accelerated
the overall reaction rates, indicating that diffusion limitations
are important parameters.658 Moreover, hierarchically meso-
macroporous zeolite nanocrystals were prepared in a quasi-
solid-state system based on the passivation concept of the
strong self-condensation of the short-chain organosilane 3-
aminopropyltrimethoxy-silane (APTES) on the surfaces of
nanocrystals.661 APTES directed the generation of zeolite
nanocrystals and guaranteed the in situ assembly of these
nanocrystals into a hierarchically micro-meso-macroporous
structure. The resultant catalysts exhibited a longer catalyst
lifetime, which was almost 8 times longer than that of the
purely microporous ZSM-5. They also exhibited a higher
propylene selectivity (41.89%). The improved adsorption
capacity was due to the abundant mesopores and macropores
in the catalysts, providing a shortened diffusion path length
and increased accessibility of reactants to active sites for
catalytic reactions.
ZSM-5 with a high mesoporosity had a high propylene
selectivity and a long catalyst lifetime during the MTP reaction
due to its improved diffusion performance and increased
tolerance toward greater coke formation.109,870−874 This
further indicated that the introduction of mesopores in zeolites
can significantly accelerate the mass transfer, inhibit the coke
deposition, and extend the catalyst lifetime.90 To gain a better
insight into the influence of the pore connectivity of zeolites in
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the MTP reaction, Mei et al.660 prepared hierarchically porous
ZSM-5 zeolites with open and closed mesopores by
desilication and templating with starch, respectively. The
introduction of open mesopores in ZSM-5 enabled the
catalysts to exhibit a high propylene selectivity (42.2%) and
propylene/ethylene (P/E) ratio (10:1). However, for the
closed mesopores that are randomly located inside the zeolite
crystals, the amelioration in propylene selectivity and P/E ratio
of the catalyst is not easily noticeable. The results
demonstrated that the creation of additional open meso-
porosity in ZSM-5 zeolite is a crucial factor in the preparation
of optimal catalysts for the MTP reaction.
In theory, a maximized molecular diffusion would be
achieved if the size of the zeolite crystal is reduced to the
single unit cell dimension.157 Hierarchical ZSM-5 zeolite with a
high-silica MFI nanosheet with an only 2 nm thickness was
successfully synthesized by using a special bifunctional organic
surfactant.659 This catalyst was an efficient catalyst with high
propylene selectivity (51.0%), high propylene/ethylene (P/E)
ratio (12.1), and long catalyst lifetime in the MTP reaction
because of its excellent diffusivity.659 Such excellent catalytic
performances were attributed to the relatively large accessible
surface area, short diffusion path length, and high mesoporosity
in the hierarchical zeolite made of the ultrathin nanosheets that
enabled it to accommodate more coke deposition, which also
contributed to the improvement in catalyst lifetime. Thus, the
reaction products could easily escape from the zeolite
micropores, and the secondary reactions, such as aromatization
and hydrogen transfer, were effectively prevented, leading to a
low deactivation rate. Besides, the relatively large accessible
surface area and high mesoporosity in the zeolite nanosheets
helped to accommodate more coke deposition, which also
contributed to the increase in the catalyst lifetime.
4.1.6.4. Methanol to Aromatics Process. Aromatics are
some of the most important fundamental raw materials in the
polymer and organic industry.875 BTX-benzene (B), toluene
(T), and xylenes (X) are the most widely used aromatic
hydrocarbons. The demand for aromatics is rapidly increasing
worldwide.876 The actual commercial processes for aromatic
hydrocarbon production are mainly based on petrochemical
processes, such as catalytic reforming or cracking gasoline
hydrogenation using crude oil.877 As a promising alternative,
the methanol-to-aromatics (MTA) process on microporous
solid acid catalysts is an important nonpetroleum route to
obtain valuable chemicals and attracted great interest.878 The
first efficient catalyst Mo-ZSM-5 for the MTA reaction was
reported in 1993.879 Since then, this reaction has been studied
by many groups. Aromatization of methanol over ZSM-5 could
be promoted by the interaction−dehydrogenation of surface
metal oxides,880 such as ZnO,881 Ga2O3,882 and SnO2.883
The performance of the catalyst in the MTA process is
greatly influenced by many conditions such as the acidic
strength,884 the pore architecture,885,886 the crystal size,887,888
and the morphology.889 Therefore, the preparation of suitable
catalysts which exhibit high diffusion and suitable acidity is
important for the MTA reaction. An effective method to
reduce the diffusion limitation is introducing additional pores
into zeolites, which can significantly facilitate the diffusion
performance of the bulky aromatic molecules894−900 and
prevent the coke deposition on the micropores901 in the MTA
process. Wang et al.662 synthesized hierarchical ZSM-5 with a
hollow structure, in which the shell was aggregated by small
coffinlike ZSM-5 crystals (Figure 43F). The synthesized
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hierarchical ZSM-5 with a hollow structure (ZSM-5-h (38))
exhibited a long catalyst lifetime of 186 h, which was 1.69
times longer than that of conventional ZSM-5 zeolite (ZSM-5-
c1) (Figure 43F,G). This was due to their much lower coking
rate than that of ZSM-5-c1 (0.0061 vs 0.0096 mg h−1).
Besides, it also exhibited a higher aromatics selectivity (40.1%)
than ZSM-5-c1 (33.9%) by suppressing the production of C5+
aliphatic hydrocarbons. Wang et al.663 synthesized a macro-
scopic bayberry-like MFI zeolite with a micrometer thick shell
and densely grown nanocrystals with an ordered packed
channel. The catalyst exhibited a higher methanol conversion
and a longer catalyst lifetime, confirming the advantage of
hierarchically porous structures in heterogeneous catalytic
reactions over pure microcrystals and nanocrystals. Zhou et
al.664 prepared various MFI zeolites with different mesoporos-
ities and acidities and systematically investigated the effects of
the mesopore quality and the acidity strength on the catalyst
performance in the MTA reactions. They found that
desilication post-treatment of zeolites can significantly increase
the mesopore volumes and decrease the strong acid density.
The resulting mesoporous catalyst can efficiently inhibit the
coke formation and increase the catalytic stability in the MTA
reaction.
4.1.6.5. Methanol Dehydration to Dimethyl Ether Process.
Generally, the dehydration temperature of methanol in the
methanol dehydration to dimethyl ether (MTD) process is
much lower than that of the MTG, MTO, and MTP processes.
Dimethyl ether (DME) is the intermediate product during the
MTH reaction, which further gets converted into olefins,
paraffins, aromatics, and other chemicals by combining with
methanol and water at high temperature.902,903 In addition to
the reaction temperature, the textural properties of catalysts
such as porosity (introduced meso-macropores), crystal size,
and morphology could also greatly influence the catalytic
performance in the MTD reaction. Currently, ZSM-5 zeolite is
the most important catalyst used in the MTD reaction.
Rownaghi et al.665 investigated the effects of crystalline size
and mesoporosity on the catalytic performance of various
mesoporous ZSM-5 zeolites in the MTD process. They found
that uniform nanocrystal catalysts showed the highest catalytic
activity and DME yield due to their reduced mass transport
resistance. Thus, it can be concluded that decreasing the
crystalline size of the zeolites is an effective way to improve
their catalytic activities in the MTD process. Hierarchically
porous ZSM-5 with intracrystalline mesopores also showed a
long catalyst lifetime and 100.0% selectivity toward DME in
the MTD process. This was due to the large mesopore volume
in mesoporous ZSM-5 that can greatly improve the coke
tolerance and thus efficiently prolong the lifetime of the
catalyst.666
In conclusion, an ideal catalyst with the stable and high
methanol conversion and product selectivity is mostly desired
in the zeolite-catalyzed methanol transformation process.
However, the slow transportation of the reactants and products
in the relatively small micropores of conventional zeolite is the
main causes for the short catalyst life. The hierarchically
porous zeolites can effectively reduce the intracrystalline
diffusion path, greatly enhance the reactants/products to and
away from the active centers, and thus improve the catalytic
conversion, inhibit the undesired secondary reaction, reduce
the coke formation, and finally extend the catalyst lifetime.
4.1.7. Catalytic Cracking Reaction. Hierarchical zeolites
are widely used in cracking reactions due to their improved
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Figure 44. (A) Schematic representation of the catalytic conversion of 1,3,5-TIPB. (B) HTEM images of Al-ECNU-7P (Si/Al = 50). Results of
catalytic cracking TIPB over (C) Al-ECNU-7 (Si/Al = 15) and (D) MCM-22 (Si/Al = 16) catalysts. Adapted with permission from ref 678.
Copyright 2016 American Chemical Society. (E) TEM images of highly crystalline FAU-type zeolites (Y-10) with nanosized particles and
octahedral morphology. (F) Conversion of 1,3,5-triisopropylbenzene over Y-10, Y-70, Y-400, and LZY-62 zeolite catalysts. Selectivity on Y-10, Y-
70, Y-400, and LZY-62 catalysts during the TIPB conversion at (G) 200 °C and (H) 225 °C. Adapted with permission from ref 280. Copyright
2015 Macmillan Publishers Limited.

diffusion of reactants and products within the hierarchical
structures of catalysts. Catalytic cracking of different types of
feedstocks, i.e., heavy fractions of crude oil, aromatic
compounds, hydrocarbons, and polyolefins, will be reported
in this section.
4.1.7.1. Fluid Catalytic Cracking Process. The fluid
catalytic cracking (FCC) process is one of the most important
conversion technologies in the oil refinery industry.904 This
process converts heavy fractions of crude oil, i.e., heavy gas oil
(HGO), vacuum gas oil (VGO), or residue feedstocks, into
useful products, such as gasoline and chemical feedstocks.905
Therefore, developing more effective FCC catalysts is of great
importance for the industrial production.906
Currently, FCC catalyst particles consist of Y zeolite, active
matrix, clays (fillers), various additives, and binders, in which
zeolite Y (FAU type) is the primary active component of the
cracking catalyst used in the FCC process due to its high
surface area, supercage structure, strong Brønsted acidity,
excellent thermal/hydrothermal stability, and low cost.907
However, the bulky molecules in heavy oil or residues have
such a large molecular dynamic size ranging from 1.2 to 15 nm
(boiling point >400 °C, carbon number >20) that they cannot
enter into the micropores of the Y zeolite (0.74 nm).205,908
Even the size of the deformed molecules allowed to penetrate
BI
into Y-zeolite pores is less than 1.02 nm.909 Only hydrocarbons
with a carbon number less than 20 can enter the micropores of
Y-zeolite, but this process cannot happen for fractions with
boiling points higher than 400 °C. Similarly, larger
intermediate molecules are tightly fitted within the micropores
and can take a relatively long time to leave the zeolite
crystal.381 The relatively long residence time leads to reduced
catalytic effectiveness and increased undesired reactions, such
as hydrogen transfer, overcracking, olefin interconversion, and,
in particular, coking.14,910,911 Thus, the desired FCC catalysts
should have improved diffusion performances and enhanced
acid site accessibility.912 These can be realized by constructing
interconnected hierarchical pore systems (pore hierarchiza-
tion),913−915 or aggregates of zeolite nanocrystals.8
Zeolite Y with well-controlled intracrystalline mesoporosity
was prepared by a surfactant templating synthesis.380 It was the
first report concerning the introduction of well-controlled
mesoporosity into Y zeolites with low Si/Al ratios. This
mesostructured zeolite Y catalyst produced much more
gasoline and light cycle oil (LCO), and less bottoms and
coke. Such improved product selectivity was due to the
mesopores introduced into the zeolites which can reduce the
diffusion limitation in the microporous zeolites.667 The larger
mesopores allow bulky reactants to access the catalytic sites
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within the zeolite crystals, thereby promoting the primary
reactions to yield more gasoline and LCO. Besides, the
mesopores facilitate the transport of the reactants and the
products in and out of the zeolite crystals, thus reducing the
undesirable secondary reactions, such as the overcracking of
the valuable gasoline and LCO to the low-value coke and dry
gases. The hydrogen transfer side reaction was also inhibited,
which contributed to higher C3 and C4 olefin yields.667
Moreover, composite catalysts based on such hierarchical
zeolite Y also showed excellent catalytic activity in the FCC
process.668 The hydrothermally stable hierarchically macro-
meso-microporous zeolite composites were prepared by the
overgrowth of ordered mesoporous Y on kaolin spheres
through the in situ assembly of preformed zeolite Y
nanoclusters on kaolin using cetyltrimethylammonium bro-
mide as soft template under alkaline conditions.668 The zeolite
Y gave micropores and mesopores in the composite and the
macroporous kaolin substrate contributes macropores. Besides,
the mesopores of the composite Y/kaolin were entirely
accessible from outside and well interconnected. The
mesopores in the catalysts can facilitate the mass transfer in
the zeolites, thus decreasing the secondary reactions resulting
in dry gas and coke formation.667 The Y/kaolin composites
exhibited a relatively low dry gas yield (1.5 wt %) and a very
low coke yield (6.9 wt %).668
Recently, the core−shell structured zeolite has attracted
great attention due to the definite reaction pathways and
excellent connection between meso- and microporosities.669
Many core−shell structured “zeolite@porous matrix compo-
sites” were developed to crack heavy oil more efficiently.671−673
A new core−shell zeolite catalyst with a hierarchical macro-
meso-micropore network was developed by controlling
overgrowth of a zeolite ZSM-5 shell on the surface of a purely
microporous Y-zeolite.670 The heavy oil was cracked step-by-
step into the required products over the designed zeolite
catalyst. The meso-macroporous shell facilitated the precrack-
ing of the large heavy oil molecules into moderate ones, which
can directly diffuse into the micropores of the Y-zeolite for
further cracking into the desired products. The results showed
that both the conversion of heavy oil and the yield of gasoline
increased when compared with conventional FCC catalyst.
4.1.7.2. Catalytic Cracking of Aromatic Compounds.
Owing to their importance and wide applications in the fluid
catalytic cracking process, the optimization of hierarchically
porous zeolites has become one of the researchers’ focuses in
recent years. Special cracking reactions were chosen to
investigate the catalytic performance of catalysts in cracking
reactions and to choose the optimum hierarchical structure.
The cracking of isopropyl benzene was chosen as a probe
reaction to study the catalytic performance and anticoking
ability of hierarchically porous zeolites. Peng et al.674 prepared
hierarchically micro-mesoporous MFI-type zeolite by steam-
assisted conversion (SAC). The precursors were confined in
the porous carbon template. The hierarchically structured
zeolite had interconnected mesopores and micropores. The
resultant hierarchically porous ZSM-5 showed a much higher
conversion (74.5 wt %) in the catalytic cracking of isopropyl
benzene than nanosized ZSM-5 (30 wt %) and bulky ZSM-5
(28.6 wt %).10
The bulky 1,3,5-triisopropylbenzene (TIPB) is regarded as a
model compound for heavy gas oil molecules, and the catalytic
cracking of 1,3,5-TIPB is widely used as a probe reaction to
estimate the improvement on catalytic performance due to
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hierarchical porosity in the zeolites (Figure 44A). 1,3,5-TIPB
has a dynamic size (9.5 Å) larger than the micropore pore size
in zeolites used for cracking reactions, such as Y, Beta, MOR,
and ZSM-5, and cannot penetrate into the internal micropore
channels.108 Thus, the cracking reactions can only be realized
at the external surface of conventional ZSM-5 zeolites. The
introduced hierarchical porosity greatly boosted the catalytic
conversion.146,675−677 For example, hierarchically micro-meso-
macroporous ZSM-5 with a house-of-cards-like structure
(HCL-ZSM-5) was prepared by a template-free zeolite
synthesis system assisted by the low-cost N-methyl-2-
pyrrolidone (NMP).262 The synthesized hierarchical ZSM-5
sample had a regular house-of-cards-like morphology (∼10
mm), which consisted of orthogonal sheetlike crystals with a
typical thickness of about 100 nm. The micro- and macropores
had a broad distribution of 5−80 nm, which mainly came from
the aggregation of zeolite nanosheets. The abundant acid sites
on the HCL-ZSM-5 were more accessible to the bulky 1,3,5-
TIPB molecules, which in turn produced greatly improved
1,3,5-TIPB conversion (90.5 wt %) when compared to
conventional ZSM-5 (15.7 wt %). The layered zeolite
precursor is a special intermediate to synthesize various
hierarchical zeolites with open mesopore structures due to its
diverse layer stackings. A swelling-type mesostructured multi-
lamellar ECNU-7P zeolite with large interlayer spacing (25 Å),
consisting of an alternative stacking of inorganic MWW zeolite
nanosheets and organic CTAB layers, was prepared through a
dissolution−recrystallization approach (Figure 44B).678 The
calcined material turned into a hierarchical zeolite catalyst (Al-
ECNU-7, Si/Al = 15) and showed improved 1,3,5-TIPB
conversion (∼72% at 1 h), which was 3 times higher than that
of the conventional MCM-22 (∼24% at 1 h, Figure 44C,D).
The cracking activity of 1,3,5-TIPB was also tested over
hierarchical ZSM-5 nanocrystals.679 The TIPB conversion
increased as the crystalline size of the zeolites nanocrystals
decreased. Their large external surface with abundant active
sites facilitated the fast cracking of bulky molecules and thus
increased the catalytic conversion of TIPB. Hierarchical Y
zeolite nanocrystals with various sizes (10 nm, sample Y-10; 70
nm, sample Y-70; and 400 nm, sample Y-400) were prepared
in the absence of template (Figure 44E).280 The abundant
intercrystalline mesopores facilitated the movement of
reactants/products to and away from the catalytically active
sites, thus leading to a superior catalytic performance and high
selectivity toward the primary dialkylated products in the 1,3,5-
TIPB cracking process (Figure 44F,G). When a hierarchical
interconnected micro-meso-macroporous ZSM-5 zeolite was
used in the 1,3,5-TIPB cracking process, its meso-macro-
porosity and interconnecting structure permitted cracking at
both internal and external surfaces and favored the access of
bulky1,3,5-TIPB molecules to the active sites, resulting in a 4-
fold increased conversion.234 These zeolitic nanocrystal
aggregates with a hierarchically micro-meso-macroporous
structure were prepared by the direct transformation of
amorphous nanoparticles into meso-macroporous aluminosili-
cates, which also acted as the support template.234 A similar
improved conversion of 1,3,5-TIPB was also found for carbon-
templated mesoporous ZSM-5 zeolite as compared with
microporous zeolite (42.1% vs 6.8%).30
As discussed above, the introduction of a hierarchical
structure into zeolites can greatly improve the catalytic
conversion. The same applies to the product selectivity. The
1,3,5-TIPB cracking is known to be a three-step successive
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dealkylation reaction in which 1,3,5-TIPB first cracks into
diisopropyl benzene (DIPB) and isopropylbenzene (IPB),
followed by DIPB cracking to IPB, and then IPB further
cracking to benzene (Bz). Side reactions such as disproportio-
nation, isomerization, and condensation also occur.680 The
effective catalytic sites for the first dealkylation of 1,3,5-TIPB
mainly happen on the external surface of the catalysts while the
further deep cracking, such as cumene to benzene, occurs
mainly on the acid sites inside the micropores.151,232,916 Thus,
the cracking extent of 1,3,5-TIPB over purely microporous
zeolites is relatively low, leading to high product selectivity to
DIPB (>50%).681 For hierarchical zeolites, the deeper cracked
products, such as benzene and IPB, become the predominant
products due to the further cracking of DIPB in 1,3,5-TIPB
cracking.108,681 The mesoporous ZSM-5 prepared by the soft
templating method exhibited a 100 wt % 1,3,5-TIPB
conversion and 100% selectivity to Bz and IPB, while
conventional ZSM-5 showed a much lower 1,3,5-TIPB
conversion (71.4 wt %) and high selectivity toward DIPB
under the same conditions.682 The high catalytic performance
of the resultant mesoporous ZSM-5 in the 1,3,5-TIPB cracking
was attributed to its open mesoporous structure and exposed
catalytic active sites. Similarly, an intracrystalline mesoporous
ZSM-5 zeolite, synthesized by employing an organosiloxane
C24H57O12NSi3 as a mesopore-directing template, exhibited an
extremely high catalytic conversion and selectivity toward Bz
which mainly came from the cracking of IPB.683 This was
attributed to the abundant accessible acid sites where the
primary products (DIPB and IPB) could further crack to
secondary products.
4.1.7.3. Catalytic Cracking of Hydrocarbons. As men-
tioned above, for a certain cracking reaction, both the catalytic
conversion and the product selectivity are improved after the
introduction of a hierarchically porous structure into the
zeolite catalysts. This also applies to the steam cracking process
of hydrocarbons with light olefins (ethylene and propylene) as
main products. Light olefins are basic raw materials for
polyethylene, polypropylene, vinyl chloride, ethylene oxide,
ethylbenzene, and other chemicals.684 The higher selectivity to
light olefins in the cracking reactions depends on the reduced
reaction path, shortened residence time, and increased
accessibility of the catalyst sites.917 Thus, hierarchically porous
zeolites with precise selectivity toward a certain product are
highly desired. Catalytic cracking of different types of
hydrocarbons will be reported in the following sections.
4.1.7.3.1. Catalytic Cracking of Naphtha. Various zeolites
such as ZSM-5, Y, and MCM-22 are used as catalysts in
naphtha cracking to produce ethylene and propylene. Among
them, ZSM-5 is considered to be the best material owing to its
unique shape selectivity that influences the preferential
formation of light olefins. Naphtha consists of different
hydrocarbons such as linear alkanes, naphthenes, isoparaffins,
olefins, and aromatics.918 These bulky hydrocarbons suffer
from severe diffusion limitations. The restricted access to the
active sites reduces the catalytic effectiveness while the slow
mass transport extends the residence time of products in the
zeolite micropores, leading to increased coke deposition and
decreased catalytic activity and selectivity toward light
olefins.919 Introducing the mesopore structure in microporous
zeolites using the principles of hierarchical structure design is
recognized as a promising route for eliminating their transport
limitations and, thus, for improving their catalytic perform-
ances. For example, a higher selectivity toward light olefins was
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achieved over a mesoporous ZSM-5 with isolated mesopores,
which was synthesized using carbon black as a mesopore
template with an average particle diameter of 12 nm. The
mesoporosity of ZSM-5 significantly enhanced the production
of light olefins (24.0 wt %), showing a 2-fold increase in
ethylene and propylene yields when compared with the
conventional ZSM-5 catalyst (13.7 wt %).920 Besides, the
reduced residence time and the fast mass transfer of
intermediate products in the mesoporous zeolites can
efficiently inhibit the olefins consuming hydrogen transfer
reactions and other secondary reactions. However, the
incorporation of carbon black into the zeolite structure created
cavelike mesopores that were not interconnected. To further
increase the selectivity toward light olefins, many efforts were
made to synthesize zeolites with interconnected meso- or
macropores. For example, using carbon nanotubes leads to the
creation of mesopore channels passing through the whole
zeolite crystal.921 A much higher olefin yield (54 wt %) was
obtained over the synthesized mesoporous ZSM-5. In the
following section, the catalytic cracking of the typical alkane
components in naphtha (C6−C8 alkanes), such as n-hexane, n-
heptane, and n-octane, used as a probe reaction to investigate
the influence of meso- or macropore quality in hierarchically
porous zeolites on their catalytic performance, is reviewed.
4.1.7.3.1.1. Catalytic Cracking of n-Hexane. The pore
structure is considered to be an essential factor to evaluate the
conversion, selectivity, and stability of the catalysts during the
cracking of n-hexane.922 Appropriate post-treatment synthesis
was necessary to develop an optimal hierarchical zeolite with a
reduced diffusion limit.922 Hierarchically porous ZSM-5
zeolites, prepared by the HF-NH4F etching method, showed
a higher BET surface area, larger mesoporous volume, fewer
defect zones, and commensurable microporous structure as
compared with the parent ZSM-5. They showed a better
catalytic performance with less carbon deposition (23 mg g−1,
which was 4 times less than that of the parent ZSM-5) due to
their large mesoporous and macroporous structure.685
Similarly, interconnected mesopores were introduced into
the as-synthesized ZSM-5 crystals by alkaline desilication with
the addition of organic amines (piperidine and hexamethyle-
nimine), which can protect the zeolite crystals from excess
dissolution and thus minimize the loss of micropores and
catalytically active sites.686 In the catalytic cracking of n-
hexane, the coke amounts formed on alkali-treated zeolites
were much lower than that of the parent zeolites. This was due
to the shortened diffusion path length offered by the
interconnection of zeolite intrinsic microporosity and the
generated mesoporosity which could effectively facilitate the
diffusion of coke precursors out of the micropores, thus
suppressing the formation of heavy coke. Thus, the primary
products also rapidly diffuse out of the zeolites, effectively
suppressing the secondary reactions.
4.1.7.3.1.2. Catalytic Cracking of n-Heptane. To inves-
tigate the effect of mesopore quality on the catalytic cracking of
n-heptane, hierarchical ZSM-5 zeolites with various intercrys-
talline mesopore volumes were prepared.687 The results
revealed that a larger mesopore volume led to a greater
improvement of selectivity toward light olefins. Zhang et al.688
further explored the effect of external acidity strength of the
hierarchical zeolites on the catalytic cracking performance.
They found that the more external acid sites are selectively
eliminated, the better catalytic performance can be achieved
due to the suppressed bimolecular reactions of ethylene and
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Figure 45. (A−L) Schematic representations and SEM images of mesoporous MFI zeolites with various mesoporous structure: (A, B) MFI-syn,
(C, D) MFI-sda, (E, F) MFI-alk, (G, H) MFI-oxy, (I, J) MFI zeolite nanocrystals, and (K, L) MFI planes. (M, N) Catalytic performance in the
degradation of HDPE over various MFI zeolites. Adapted with permission from ref 702. Copyright 2011 Elsevier.
propylene and the inhibited coke formation. Besides, the
addition of ZRP-1 zeolite (50 wt % loading), which is an MFI
structure zeolite containing rare earth elements and
phosphorus, during the hydrothermal synthesis of ZSM-5
zeolite yielded composite zeolites with bimodal porosity.689
The aggregation of zeolite nanocrystals resulted in hierarchi-
cally porous ZSM-5-ZRP-1 zeolites with an interconnected but
disordered mesoporous structure (15−55 nm), which were
more active than conventional ZSM-5 zeolites and more
selective toward ethylene and propylene than conventional
ZRP-1 zeolites in the cracking of n-heptane.
4.1.7.3.1.3. Catalytic Cracking of n-Octane. Highly
crystalline mesoporous IM-5 zeolite, prepared by alkaline
treatment, exhibited a higher light olefins yield (especially
propylene) and longer catalyst lifetime in cracking n-octane
than conventional ZSM-5 zeolites.690 Similarly, the alkali-
treated MFI zeolites also showed a greatly improved catalytic
activity and high selectivity toward propene in the cracking of
n-octane.691 The addition of mesopores formed during the
alkali treatment can efficiently suppress the production of long-
chain alkanes. The cracking activity of n-octane was also tested
over hierarchical ZSM-5 zeolite nanocrystals.692 The catalyst
showed an extended catalyst lifetime as compared to the
microporous ZSM-5. Such a higher catalytic stability was
attributed to the fast diffusion of reactants in a hierarchically
porous system. A zeolite composite with MFI and MOR
zeolite structures was also investigated.693 The existence of
intracrystalline mesopores (4 nm, created in MOR zeolites)
and macropores (50−100 nm, formed by the polycrystalline
aggregation) in the zeolite composite facilitated the molecular
transport and increased the active-site accessibility, thus
leading to a higher catalytic activity in the cracking of n-octane.
4.1.7.3.2. Catalytic Cracking of C4 Alkene. Hierarchically
porous zeolites are also used in the cracking of low-valued C4
olefin to produce high-valued propylene. The relatively fast
mass transport facilitates the primary product out of the
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zeolites and effectively suppresses the hydrogen transfer
reactions that produce aromatics and alkanes, which lowers
the yield of targeted propylene and accelerates the catalyst
deactivation. Hierarchically structured ZSM-5 zeolites, which
were synthesized by a mesoporogen-free steam-assisted
crystallization procedure, showed an enhanced propylene
yield (40 wt %) when compared with the microporous ZSM-
5 (27 wt %).694 Mesoporous ZSM-5 was prepared by alkali
treatment and applied in butene catalytic cracking.695 The
introduced mesopores effectively increased the accessible
active sites and facilitated the product molecule out of the
zeolites, thus leading to an improved catalytic performance.
The selectivity of ethylene and propylene over the mesoporous
ZSM-5 reached 81.76% while, for the conventional ZSM-5
zeolite, the corresponding value was only 39.37%. Similar
results were found for surface silicon-rich hierarchically porous
ZSM-5, which was prepared by hydrothermal dealumina-
tion.696 They exhibited an excellent catalytic performance and
high selectivity toward propylene and ethylene in the cracking
of butylene, which was attributed to their abundant
mesoporosity and large external surface. Arudra et al.697
reported that Silicate-1 zeolite is an efficient catalyst for
propylene production from 1-butene cracking due to the
absence of strong acid sites. Based on this conclusion, they
further modified the surface of ZSM-5 by silica deposition
using the chemical liquid deposition method and synthesized a
hierarchically porous silicalite composite material with a core−
shell structure by the hydrothermal method.698 The propylene
yield and the selectivity toward light olefins were higher on this
core−shell silicalite composite than on silica deposited ZSM-5,
which was prepared via the chemical liquid deposition (CLD)
method. The increased selectivity was attributed to their large
mesopore voids, which reduced the hydrogen transfer reactions
that form alkanes and aromatics.
4.1.7.4. Catalytic Cracking of Polyolefin. Plastic waste is of
great environmental concern worldwide. The main compo-
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nents of plastic waste are polyolefins, consisting of low-density
polyethylene (LDPE), high-density polyethylene (HDPE), and
polypropylene (PP).923 The recycling of plastic waste is a
highly challenging task since the carbon chain is typically in the
range of tens of thousands. The catalytic cracking of
polyolefins over zeolite catalysts to useful products such as
fuels or chemicals is a good option.924 Hierarchically porous
zeolites used for this purpose showed a high potential in
solving this important environment problem.925,926 In the
cracking process, large molecules in polyolefins cannot enter
into the micropores, and thus, the catalytic degradation of
polyolefins first takes place on the external acidic sites of the
zeolite catalysts. The catalytic activity of the catalysts strongly
depends on their external surface area.927 For example,
hierarchical ZSM-5 aggregates, synthesized by the addition of
surfactant, exhibited excellent catalytic activity in LDPE
cracking.699 The improved catalytic performance in the
reactions involving large molecules was attributed to the
improved accessibility to the active sites. Similarly, the
introduction of mesopores into Beta zeolites by silanization
significantly increased the catalytic cracking degree of
HDPE.700 Besides, hierarchically porous ZSM-5 zeolite
nanocrystals with abundant intercrystalline mesopores also
exhibited a remarkable catalytic activity in the LDPE cracking
reaction.701 The catalyst with more accessible acid sites and
higher acid strength provided an improved catalytic activity
under mild conditions. In the sequential detemplation−
desilication process, Perez-Ramirez et al.497 also found that
the excellent catalytic cracking performance resulted from the
suitable treatment of the zeolite to generate mesoporosity
while maintaining the crystallinity and intrinsic acidity.
Furthermore, the interplay between the overall catalytic
cracking performance in LDPE cracking and the large external
surface of hierarchical zeolite ITQ-4 was investigated.321 The
hierarchy factor (HF) was appropriately related the introduced
mesoporosity to catalytic activity.13 To optimize the
hierarchical structure, the HF needs to be maximized,
comprising the increase of the mesopore surface area without
a severe sacrifice of the micropore volume. It was found that
the optimal activity in LDPE cracking required both a large
mesoporous surface area and suitable Brønsted acidity.
Therefore, the amount of the introduced mesoporous porosity
should be weighted carefully against the compromised
microporosity. Furthermore, Lee et al.702 investigated the
contribution of mesopores on the catalytic degradation of
HDPEs. They prepared four mesoporous MFI zeolites with
different mesopores by treatment with an alkaline solution
(MFI-alk), the addition of a special structure-directing agent
(MFI-sda) and an oxyacid (MFI-oxy), and the synthesis of a
mesoporous material from a synthetic mixture containing
dissolved MFI fragments (MFI-syn) (Figure 45A−L). The
conversion of HDPE was very fast on MFI-sda, MFI-alk, and
MFI-syn, and 100 wt % conversion was achieved in 60 min,
while the degradation on MFI-oxy was slow due to its small
pore volume (Figure 45M,N). This was indicative of the fact
that the characteristics of mesopores were important in
determining catalytic activity.
In conclusion, the catalytic performance for the catalytic
cracking reactions of bulky molecules are strongly correlated
with the accessibility of the catalytically active sites, which is
decided by both the pore size and the pore connectivity in the
zeolites. However, the internal diffusion limitations within the
micropores leads to severe pore blocking and delayed mass
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transport. Therefore, considerable effort has been devoted to
synthesize hierarchically porous zeolites for alleviating the
diffusion limitations. Hierarchically porous zeolites with
abundant meso- or macropores that are directly accessible
from the outer surface of the zeolite crystal are highly desired
for the catalytic cracking reactions.
4.1.8. Biomass Conversion. Growing demand for
sustainable fuels and chemicals has renewed the interest
toward alternative feedstocks replacing crude oil in traditional
refineries. Thus, biomass, as the only renewable carbon source,
has attracted great attention in the past several decades.928 It
can be divided into two main categories: lignocellulose
feedstock and oleaginous feedstock. Typically, biomass
conversion is the decomposition of bulky biopolymers into
small basic molecules and/or the further processing of small
basic molecules to value-added end-products. Microporous
zeolites with various structures, such as MFI,929 USY,87,704
Beta,706 and MOR,708 were employed to catalyze the biomass
conversion. For each process, the accelerated diffusion
performance and the improved accessibility toward active
sites are the determining factors. Hierarchically porous zeolites
play an important role in many biomass conversions.
4.1.8.1. Lignocellulose Biomass Conversion.
4.1.8.1.1. Lignocellulose Biomass Feedstock Processing.
4.1.8.1.1.1. Lignocellulose to Bio-Oils. Lignocellulose biomass
is the most abundant biomass resource and consists of three
polymers (cellulose, hemicellulose, and lignin) and extractives
(terpenes, etc.). Most of the biomass-derived materials exhibit
low density, making them difficult to store and transport. One
way to overcome this limitation is to increase biomass
density.930 Cracking or pyrolysis is probably the most efficient
method to increase the energy-density of these renewable
materials. Bio-oil, which is considered as the energy-dense
form of biomass, can be produced by a catalytic pyrolysis
treatment. Hierarchical zeolites are the most promising
catalysts for biomass pyrolysis. The increased external surface
area and the improved diffusion performance in the zeolite
crystal can greatly boost its catalytic activity and thus result in
high-quality bio-oils and lower coke yields, as observed for
hydrolysis of (hemi)cellulose,931,932 catalytic fast pyrolysis
(CFP) of lignocellulose,703 cellulose,929 Miscanthus,929 and
lignin.933 The hierarchical zeolites exhibit slower deactivation
of the active sites, shorter retention time of products in the
micropores, and less secondary coke product formation.934 For
example, a better catalytic stability was reported for the CFP of
lignocellulose with mesoporous ZSM-5 zeolites prepared by
desilication with NaOH solutions, in which only a lower
amount of coke was deposited.703
Lignocellulose to Platform Molecules. The transformation
of lignocellulosic biomass to small useful molecules can be
realized by the following process: the controlled lignocellulosic
(lignin, cellulose, and hemicellulose) depolymerization to
simple sugars and subsequent sugar transformations to targeted
molecules. These molecules are regarded as the platform
materials for the production of polymers, fine chemicals, and
transportation fuels. Among these platform molecules, 5-
hydroxymethylfurfural (5-HMF) and levulinic acid (LA) are of
special interest.
The major component of the lignocellulosic biomass is
cellulose (40−50 wt %), and its structural unit is glucose. 5-
HMF, obtained from the dehydration of glucose708,935,936/its
isomer fructose704,706,937 or the direct dehydration of
cellulose,705,707 is a value-added chemical and has various
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applications in chemicals and fuels.938 As an isomer of glucose,
fructose could be rapidly dehydrated to HMF. Yang et al.706
synthesized a hierarchically porous Beta zeolite single crystal
via the steam-assisted crystallization of a carbon−silica
composite monolith. The resultant catalysts composed of
connected nanoparticles were applied for the dehydration of
fructose to 5-HMF. The conversion of fructose over hierarchi-
cally porous Beta reached 100 wt % in 2 h with an HMF yield
of 78.5 wt % while, over conventional Beta, the reaction time
for the total conversion of fructose was increased to 3 h, and it
was achieved with a lower HMF yield (58.7 wt %). The greatly
improved catalytic performance over hierarchically porous Beta
zeolite was due to the free and efficient diffusion of bulky
molecules and the high accessibility of external acidic sites.
Similar observations were found on hierarchical USY zeolite
and ZSM-5 zeolite, which also exhibited higher selectivity
towards 5-HMF in the dehydration of fructose than that of the
conventional ones.87,704 The conversion of fructose to 5-HMF
is easier than that of glucose due to the presence of the
furanose group. However, the high cost of fructose limits their
further applications. Thus, the direct conversion of glucose to
5-HMF has attracted increasing attention. It was reported that
a combination of micropores and mesopores was helpful in
increasing the yield of 5-HMF from glucose.936 Velaga and
Peela708 observed that the mesoporous MOR exhibited
excellent catalytic activity towards glucose dehydration to 5-
HMF with a selectivity to 5-HMF of 87% at a glucose
conversion of 76 wt %. The high yield and selectivity to 5-
HMF with minimal side products were due to the introduced
mesoporosity and the optimized amount of Lewis and
Brønsted acid sites in the catalysts. Hierarchically porous
zeolite catalysts were also designed to efficiently convert
cellulose to HMF. Nandiwalet et al.705 prepared 5-HMF from
cellulose over desilicated zeolite ZSM-5, which gave a cellulose
conversion of 67 wt % and a 5-HMF yield of 46 wt % at 190
°C in 4 h. Dealuminated zeolite Beta with tunable Brønsted
and Lewis acid site distribution and mesoporosity improved
the conversion of cellulose to 5-HMF with similar results to
those obtained by Nandiwalet et al. with desilicated ZSM-5.707
The catalyst exhibited a 42 wt % yield of 5-HMF with a full
conversion of cellulose at 200 °C in 5 h. Moreover, the
consecutive rehydration of 5-HMF generated levulinic acid
(LA), another important intermediate.939 The yield of LA
obtained from glucose over a micro-mesoporous catalyst
composite (with ZSM-5 crystalline structure) was almost
doubled (36 wt %) compared with the parent material.940
Terpene Transformations. Terpenes refer to extractives,
consisting mainly of α-pinene (60−85 wt %).941 Considering
the abundance of α-pinene in inexpensive turpentine oil, its
conversion to more valuable chemicals is of great interest. α-
Pinene can be converted into a variety of important chemical
intermediates, like terpinene, camphene, limonene, or cymenes
that are essential for the synthesis of many fine chemicals.942
The dominant factor influencing the conversion of the bulky
biomass molecule is the catalyst lifetime influenced by coke
formation that possibly blocks the micropores.943 The
hierarchical zeolites have an extended catalyst lifetime since
the larger external surface area gives a slower deactivation, and
the shorter retention time of products in the zeolites results in
lesser secondary coke formation. To improve the catalytic
performance of the conventional ZSM-5 zeolites, mesopores
were introduced into ZSM-5 zeolite by desilication treatment
with NaOH.320 The resultant catalysts displayed an increased
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α-pinene conversion from 11 to about 27 wt % when
compared with conventional ones.944 Similarly, a lower
amount of deposited coke over hierarchical USY, ZSM-5,
and Beta zeolites was also reported in the isomerization of α-
pinene.709,710,945 The importance of mesopores in boosting
catalytic properties was also confirmed by another successful
application of mesoporous H-ferrierite. The zeolite exhibited
an improved α-pinene conversion (from 72 to 97 wt %) and an
increased selectivity towards limonene.946
4.1.8.1.2. Lignocellulosic-Based Feedstock Processing.
The usage of lignocellulosic biomass in a refinery can be
accomplished in different ways. An effective option is the
conversion of lignocellulosic biomass to a fluid by pyrolytic
treatment, leading to the production of a liquid called bio-oil.
The bio-oil is a highly oxofunctionalized mixture of light-to-
medium hydrocarbons with a high oxygen content, high
viscosity, and low stability. To widen their potential
applications, oxygen must be removed by hydrodeoxygenation
(HDO) processes, such as hydrodehydration and hydro-
decarboxylation.947 It was reported that bifunctional catalysts
containing both the metal nanoparticles and acidic zeolites
favored the catalytic hydrodeoxygenation of pyrolysis oil.947
Hierarchical zeolites with introduced mesopores or macro-
pores are promising candidates as HDO catalyst supports due
to the large size of lignocellulosic biomass. The meso- or
macroporosity can enhance the dispersion of the metal phase
and improve the accessibility of the relatively bulky reactant
molecules to the active sites.948,949 Veses et al.949 investigated
the metal-loaded hierarchically structured mesoporous ZSM-5
zeolites as catalysts for the deoxygenation of bio-oil. The
mesopores were introduced by desilication. The hierarchical
zeolites after impregnation with different metals (Sn, Cu, Ni, or
Mg) exhibited an increased deoxygenation compared to the
parent acidic hierarchical zeolite. The Mg-loaded hierarchical
zeolite led to the production of fuels with the best
characteristics, achieving the greatest reduction in the oxygen
content and the lowest acidity.949 Also, the hierarchical
porosity in the zeolites plays a dominant role in deciding the
cracking degree of the desired fraction and avoiding the
unwanted byproducts in the HDO reactions involving acid-
catalyzed bond-cleavage.169,378,950 These advantages were
observed in the upgrading reactions of bio-oils with desilicated
Y zeolite.711 The catalysts showed an increased selectivity
toward primary cracking and deoxygenation products and
decreased selectivity toward aromatic hydrocarbons due to the
suppressed possibility of secondary oligomerization, cycliza-
tion, and hydrogen transfer reactions.
4.1.8.2. Oleaginous Biomass Conversion. 4.1.8.2.1. Trigly-
ceride Processing. Oleaginous feedstocks, such as animal fats
and vegetable oils, are completely composed of triglycerides
and are mixtures of esters made by glycerol and fatty acid alkyl
(varied in alkyl-chain length and number of unsaturated
bonds).951,952 Generally, triglycerides cannot be used directly
as combustible fuels due to their high viscosity and low
volatility. Thus, the processing of triglyceride-rich biomass in
chemical reactions such as transesterification, catalytic
cracking, or pyrolysis represents a promising future option to
replace the limited petroleum resources with biofuels and
chemicals.953 In particular, the transesterification of triglyceride
in the presence of a short-chain alcohol, such as methanol or
ethanol, can produce biodiesels that are considered to be an
important renewable source to alternative diesel fuel.954,955
Hierarchically porous zeolites were proven to be excellent
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Figure 46. (A−D) HAADF-STEM images of hierarchical zeolite materials with different mesoporous structures (the insets are the schematic
illustrations of the pore structures for visualization): SEM image of (A) H-Z5-1, (B) H-Z5-2, (C) H-Z5-3, and (D) H-Z5-4. (E) Glycerol
conversion vs time on stream over a series of hierarchically porous ZSM-5 in the dehydration of glycerol to acrolein. (F−I) Plots of various
structure−performance relationships for CZ5 (black), H-Z5-1 (red), H-Z5-2 (blue), H-Z5-3 (magenta), and HZ5-4 (cyan), where the
mesoporosity parameters of Vmeso,N2, Vmeso,Hg, and Smeso are associated with the catalytic performance of lifetime on the left (circle, at 320 °C) and
initial activity on the right (triangle, at 250 °C; cubic, at 280 °C). The catalyst lifetime is defined as the time for which the conversion exceeds the
80%, while the initial activity is defined as the glycerol conversion at the initial reaction period of 2−3 h. Adapted with permission from ref 719.
Copyright 2015 American Chemical Society.

catalysts with a high catalytic efficiency in the transformation of
triglyceride. The introduction of secondary mesopores or
macropores into the zeolite frameworks can significantly
improve the accessibility of bulky triglycerides to the active
sites and thus boost the conversion efficiencies,956 as observed
in the conversion of crude vegetable oil (palm oil) by Ni/
HBEA712 or Pt/HBEA,713 rapeseed by Ni/ZSM-5,714 used
vegetable oil (waste cooking oil) by NiMo/USY715 or Ni/Y,716
animal fats (fish oil) by Ga/MFI,717 and nonedible oil
(safflower oil and microalga oil) by USY957 and NiMo/
ZSM-5,958 respectively. For example, Verma et al.958 employed
mesoporous zeolite ZSM-5 and Ni−W metal components as a
composite catalyst and found that the hierarchically structured
catalyst showed a high yield of C9−C15 hydrocarbons (40−
45%) and high isomerization selectivity (isomer/n-alkane, i/n
∼2−6) from Jatropha oil. However, the Ni−W/SiO2−Al2O3
catalyst could only yield ∼33% of jet-range hydrocarbons but
with low selectivity to the isomers (i/n ∼1.1).
4.1.8.2.2. Glycerol Processing. The transesterification of
triglycerides to biodiesels generates large amounts of glycerol
byproducts.959 Thus, the conversion of glycerol into value-
added chemicals has attracted great attention.960 Many
glycerol transformation methods which have been developed
like dehydration, acetalization, etherification, and aromatiza-
tion will be discussed in this section.
4.1.8.2.2.1. Glycerol Dehydration. The dehydration of
glycerol to acrolein is an important reaction.961 Possato et
al.718 investigated the catalytic performance of mesoporous
BO
ZSM-5 zeolite and found that the catalytic life is greatly
improved by the increased mesopore volume in the catalyst.
Zhang et al.719 further investigated the influence of mesopore
quality on the catalytic performance. A series of ZSM-5 zeolites
with various mesopore structures were prepared, including
bulky ZSM-5 with fewer closed intracrystalline mesopores (H-
Z5-1), nanosized ZSM-5 with more closed intracrystal
mesopores (H-Z5-2), oriented self-assembled ZSM-5 nano-
crystals with abundant open intercrystalline mesopores (H-Z5-
3), and self-assembled ZSM-5 nanocrystals with intra- and
intercrystalline mesopores (H-Z5-4) (Figure 46A−D). The
conventional ZSM-5 (C-Z5) catalyst suffered from the fastest
deactivation after 3 h. The catalytic conversion over C-Z5 even
decreased to less than 45 wt % after 8 h. This was due to the
extremely slow diffusion. In contrast, the incorporation of
mesopores within microporous zeolites prolonged the catalyst
lifetime (comparing H-Z5-x with C-Z5). All of the four
hierarchically structured catalysts showed slower deactivation
than C-Z5 (Figure 46E). The H-Z5-3 and HZ5-4 samples with
open and interconnected mesopores exhibited a longer catalyst
lifetime than H-Z5-1 and H-Z5-2 samples containing isolated
intracrystalline mesopores. This is due to the facilitated mass
transfer and hindered coke formation offered by open and
interconnected mesopores. The relationships between the
catalytic performance (lifetime and initial activity) and the
structural properties (Vmeso,N2, Vmeso,Hg, and Smeso) are shown in
Figure 46F−I. This further confirmed the positive role of the
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mesopores on extending the catalyst lifetime and increasing
catalytic activity. Figure 46F,G shows the relationship between
the catalyst lifetime and total mesopore volume (Vmeso,N2). The
lifetime increased with increasing Vmeso,N2. The structural
parameter of Vmeso,Hg indicated the accessible mesopores by
mercury intrusion from the zeolite outer surface (Figure
46H,I). The relationship between lifetime and Vmeso,Hg
excluded the influence of closed mesopores. The longest
catalyst lifetime was observed for H-Z5-3 and H-Z5-4. It
further confirmed that the sole existence of closed mesopores
in ZSM-5 zeolites can also extend the catalyst lifetime. Besides,
the mesoporous zeolites also exhibited higher selectivity
toward acrolein than C-Z5. It was noteworthy that the open
and interconnected mesopores (H-Z5-3 and H-Z5-4) are more
effective than closed ones (H-Z5-1 and H-Z5-2). The presence
of small intracrystalline mesopores could result in a reduced
lifetime and decreased catalytic activity (H-Z5-2 < H-Z5-1 <
H-Z5-4 < H-Z5-3). This catalytic property was due to the pore
condensation of glycerol or its heavier derivatives.719
4.1.8.2.2.2. Glycerol Acetalization. The catalytic activity of
zeolites in glycerol acetalization can be greatly improved by the
fabrication of a hierarchical porosity.962 For example,
mesoporous zeolite Beta, prepared by the dealuminated
method, exhibited an improved catalytic activity due to the
accelerated mass transfer and enhanced accessibility provided
by the mesopores and the controllable acidity offered by the
dealumination treatment. It was noteworthy that the reduction
of crystalline size of the zeolite can greatly improve the
catalytic activity and selectivity toward the dioxolane product
when using Beta zeolite720 and ZSM-5 zeolite721 as catalysts.
4.1.8.2.2.3. Glycerol Etherification. The etherification of
glycerol is an important reaction aimed at producing
oxygenated blending stocks as diesel fuels.963−965 The acid
strength and porosity of the catalysts have a great impact on
the glycerol conversion and the selectivity toward desirable
products. A treatment of HY zeolite with citric or nitric acids
resulted in the generation of mesopores in which the citric acid
created pores with a diameter larger than 3 nm, and nitric acid
produced pores with a diameter less than 3 nm. These
mesoporous zeolites showed improved catalyst acidity.722
Consequently, increased glycerol conversion and selectivity
toward di-tert-butylglycerols were observed. Similarly, Saxena
et al.723 reported that the use of mesoporous Beta zeolite led to
a higher glycerol conversion (98 wt %) than conventional Beta
(85 wt %), demonstrating the superior catalytic performance of
the mesoporous Beta in the etherification of glycerol.
4.1.8.2.2.4. Glycerol Aromatization. The development of a
new approach for synthesizing aromatics by glycerol
conversion has attracted great attention. Hoang et al.724
confirmed that ZSM-5 zeolites provided a higher aromatic
conversion than other types of zeolite catalysts due to their
suitable microporous structure and acidity. However, ZSM-5
suffered rapid deactivation due to heavy coke deposition. The
catalytic lifetime can be significantly extended after the
introduction of mesopores into the ZSM-5 zeolites. For
example, mesoporous ZSM-5 zeolites synthesized by Xiao et al.
exhibited a nearly 2-fold increase in benzene, toluene, and
xylene (BTX) yield and a 3-fold improvement in catalyst life as
compared to conventional microporous ZSM-5 (13.9 wt %
BTX yield and 4 h catalyst life).725 Such superior catalytic
properties were attributed to the mesopores in the ZSM-5
catalyst. One possible source of the aforementioned challenges
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may be the presence of transport limitations in the catalyst
pore structure. Bulky oxygenates formed during the initial
stages of pyrolysis may not be able to efficiently reach the
active sites within the catalyst micropores. Application of a
mesoporous catalyst can be advantageous, as enlarging the
pore structure results in increased accessibility of reactants to
catalyst acid sites.
In conclusion, biomass conversion generally involves the
conversion of a broad range of chemical species with different
sizes. Obviously, the accessibility of the active sites by the
reactants in the catalysts is of great importance, and many
efforts are made to enhance the transport of the reactant and
product to and away from the active sites. Besides, in the
biomass conversion, the tunable pore size and pore
architecture of hierarchically porous zeolites offer great
possibilities for the conversion of various biomass-derived
feedstocks. Thus, it can be concluded that the rational design
of the hierarchically porous zeolites with improved mass
transfer, inhibited undesired transformations, and reduced
catalyst deactivations is of great importance.
4.1.9. Conclusion. As discussed in section 4.1, catalytic
applications of hierarchical zeolites are tested in different
industrially relevant reactions, such as the Friedel−Crafts
reaction, the Beckmann rearrangement, the Fischer−Tropsch
synthesis process, the hydroconversion process, the oxidation
reaction, the transformation of methanol, the catalytic cracking
reaction, and the biomass conversion. The hierarchical zeolite
catalysts exhibited superior catalytic activity, selectivity, and
lifetime when compared with microporous zeolites, which is
due to their optimal mesopore quality, such as the size,
distribution, and connectivity of mesopores inside the crystals.
Depending on the synthesis approaches enumerated in section
2, quite diverse geometries of the imbedded meso- or
macropores are obtained in the hierarchically porous zeolites,
ranging from isolated mesovoids to open mesoporous channels
through the whole microporous crystal. In turn, different
geometries with different interconnectivities lead to notably
different mass transfer patterns. Thus, investigating the
structure−performance relationships in these zeolites with
multiple porosities is vital to improve their catalytic properties.
However, it still remains a great challenge. More importantly,
most previous studies reported that the improved catalytic
performances of hierarchical zeolites are due to the enhanced
mass transfer, but they failed to present direct evidence of
diffusion characteristics. Thus, the diffusion on hierarchical
zeolites should be further studied to confirm the advantages of
the hierarchically porous system in hierarchical zeolites.
4.2. Environmental Applications
4.2.1. Wastewater Treatment. Removal of biotoxic heavy
metals, such as Sr2+ and Hg2+, from the industrial wastewater
has attracted great attention worldwide due to their damaging
impact on the environment and public health. The adsorption
and ion-exchange approaches are the simplest and most
effective methods to remove harmful elements from con-
taminated industrial water. Generally, zeolites are efficient
adsorbents/ion exchangers in wastewater treatment across a
wide range of contaminants.966 Zeolites with a low Si/Al ratio
such as NaA and NaX zeolites were used to remove heavy
metal ions, such as Cs+,967 Sr2+,967 and Zn2+,968 from water by
an ion-exchange process due to the high concentration of
exchangeable nonframework cations available in their micro-
porous structure.967,968 However, their ion-exchange capacity
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was still affected by the diffusion limitation in the microporous
network. The hierarchical zeolites are considered to be ideal
materials for ion exchange due to their significantly superior
ion-exchange performance. For example, a hierarchically
structured porous composite constructed by clinoptilolite
supported on date stone carbon was prepared by fixing a
natural zeolite (clinoptilolite) on the porous date stone carbon
or by direct hydrothermal method on the surface of porous
date stone carbon to offer a supported high-surface-area ion-
exchange material to remove metal ions from aqueous streams.
Sucrose and citric acid were used as a binder to fix the
clinoptilolite. The hierarchically structured composite ex-
hibited a much higher ion exchange capacity of Sr2+ ions
from an aqueous solution than that of conventional
clinoptilolite.969 Similarly, the hierarchical zeolite X/diatomite
composite was prepared by the hydrothermal synthesis of a
zeolite X layer over diatomite.970 Both hierarchically porous
zeolite X composites exhibited a significantly improved ion-
exchange behavior for manganese ion removal when compared
with purely microporous zeolites X. Moreover, Fardmousavi et
al.971 prepared the thiol-functionalized Beta zeolite/MCM-41
mesoporous silica nanocomposites and then grafted them with
3-mercaptopropyltrimethoxysilane. The hierarchically porous
zeolite/MCM-41 composite was employed in the extraction of
Hg2+ from aqueous solutions. The material showed an
excellent capacity for the Hg2+ ion exchange from aqueous
solutions, kinetically fast adsorption process, and extremely
short equilibrium state. A maximum ion-exchange capacity of
8.2 mequiv g−1 was obtained with the hierarchical zeolite/
MCM-41.
4.2.2. Adsorptive Desulfurization. Conventional hydro-
desulfurization (HDS) is widely used in the refinery to remove
most aliphatic sulfur compounds such as sulfides, disulfides,
and mercaptans. However, the HDS reaction is less efficient for
aromatic refractory sulfur compounds such as thiophene (TP),
benzothiophene (BTP), dibenzothiophene (DBTP), and their
derivatives. New technologies have been developed to realize
the ultradeep desulfurization.972 Among these, adsorptive
desulfurization is regarded as a promising technology in the
selective removal of thiophenic sulfur compounds under
moderate conditions.973 It is based on the physisorption or
chemisorption process of organosulfur compounds on ion-
exchanged zeolites. The highly dense Brønsted acid sites in the
zeolites act as an adsorption platform by donating a proton to
the nearby adsorbate molecules. Deep adsorptive desulfuriza-
tion is decided by the charge of metal cations, the acid
properties of the zeolites, the Si/Al ratio, and the pore size of
the zeolites. The utilization of zeolites as liquid-phase sulfur
adsorbents is receiving significant attention. The removal of
sulfur from hydrocarbon fuels can be an ideal desulfurization
method due to the low energy and low cost of such a process.
However, diffusion constraints within the micropore structure
of zeolites can significantly reduce their adsorption capacity,
especially when bulky sulfur compounds are present in fuels.
Hierarchical zeolites showed high performances in the
desulfurization of liquid fuels. The introduction of meso-
porosity into zeolites allows for bulky sulfur compounds, such
as DBT and 4,6-DMDBT, to enter the zeolite micropores, thus
improving accessibility to the active sites. Tian et al.974
investigated the sulfur removal from a model fuel containing
various thiophenic compounds and found that hierarchical H-
Beta zeolite by desilication removed about twice as much total
sulfur when compared with the parent Beta zeolite. However,
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the SiO2/Al2O3 ratio of zeolite Beta is much higher than that of
Y, thus limiting the amount of metal ions in Beta zeolite
introduced by ion exchange, which are the main adsorption
sites for the adsorption of sulfur aromatic compounds. They
further developed a novel desulfurization sorbent based on Y
zeolite that exhibited a high sulfur capacity and low mass
transfer resistance.975,976 The metal-exchanged hierarchical Y
zeolite containing abundant mesopores to improve diffusion
performances and large external surface area provided
abundant active sites for sulfur adsorption. Bimetals were
introduced into hierarchical Y zeolites to further enhance the
selective adsorption of sulfur compounds from a model fuel
mixture. Wang et al.977 demonstrated that the desulfurization
performance of hierarchically porous NiCe-exchanged zeolite
Y in removing DBTP was higher when compared with Ni-
exchanged zeolite Y and Ce-exchanged zeolite Y. Wang et al.978
further investigated the role of the mesoporosity in CuCe
mesoporous Y zeolites on the desulfurization process. Such
bimetallic mesoporous Y zeolites exhibited a DBTP capacity 5
times more than parent Y due to both improved mass transfer
and high adsorption energy.
In conclusion, the synthesis and modification of zeolite-
based adsorbents have received considerable attention in
adsorptive desulfurization. Zeolites showed a high sulfur
loading capacity, easy regenerability, and a stable crystalline
structure for adsorptive removal of sulfur compounds. It is
highly advantageous in the removal of small molecules in
various adsorption applications. However, their relatively small
micropores restrict the transfer of the bulky aromatic refractory
sulfur compounds, such as DBTPs and other alkyl-branched
dibenzothiophenes. Hierarchically porous zeolites with intro-
duced meso- or macropores have been utilized for the
adsorptive desulfurization. The meso- or macropores shorten
the diffusion path to the internal active sites of the zeolite,
which are beneficial for the interaction with bulky molecules.
4.2.3. CO2 Capture. Capturing carbon dioxide is of great
importance to mitigate climate change resulting from green-
house gas emissions.979 Recent studies reported that the
adsorption processes using hierarchically micro-mesoporous
zeolites are a promising technology for CO2 capture because
they possessed a larger surface area to allow for increased
adsorption of CO2.980,981 Gong et al.982 reported a biosyn-
thesis route to prepare hierarchically porous SAPO-34
constructed by nanosheets. The obtained hierarchically porous
SAPO-34 showed a distinctive morphology with nanosheets
and gaps between nanosheets, giving rise to a blooming
flowerlike structure. This hierarchically porous SAPO-34
exhibited a much higher CO2 adsorption capacity of 2.77
mmol g−1 at 100 kPa with the CO2/CH4 ideal separation
factor of 8.2 as compared to the conventional SAPO-34. It
took 6.1 min for CO2 to reach the adsorption equilibrium,
which was much faster than conventional SAPO-34 due to the
nanosheet-constructed porous structure. By combining sacri-
ficial templating and freeze-casting techniques, Besser et al.
synthesized hierarchically porous zeolite 13X monoliths.983
The hierarchically porous monoliths exhibited a high working
capacity and a fast CO2 uptake when compared with
commercially available zeolite 13X. Ojuva et al.984 synthesized
hierarchical macro-microporous zeolite 13X with a laminar
structure by the freeze-casting method. The zeolite showed a
high and rapid CO2 adsorption. This hierarchical zeolite 13X
exhibited a very fast initial uptake, in which more than half of
the maximum uptake was achieved within 15 s. Moreover,
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Figure 47. TEM images of (A, B) MFI and (C, D) BEA type zeolites with different morphologies. Adsorption kinetics of n-hexane in (E) MFI-type
zeolites and (F) BEA type zeolites with various morphologies (at 25 °C, p/p0 = 0.5). Adapted with permission from ref 995. Copyright 2016
American Chemical Society.
ZSM-5 has a good affinity for the CO2 molecule, and the
desorption of CO2 from ZSM-5 can be controlled under mild
conditions.985 Hierarchically porous ZSM-5 with a large
surface area and an introduced mesoporous structure is
expected to be a high-performance adsorbent for CO2
removal.986 Thus, Liu et al.987 developed hierarchically porous
ZSM-5 using organosilanes as templates and found that the
CO2 adsorption capacity was much higher than that of the
microporous ZSM-5. The effective improvement of CO2
adsorption mainly originated from the large surface area,
which promoted the CO2 adsorption capacity.
4.2.4. Removal of Volatile Organic Compounds. The
removal of volatile organic compounds (VOCs), mainly
consisting of aromatic hydrocarbons and aldehydes, is an
urgent necessity since these compounds are harmful for the
environment and human health.988 Advanced technologies for
reducing VOCs have been well developed, such as
adsorption989,990 and catalytic combustion.991−993
4.2.4.1. Adsorption of Volatile Organic Compounds. MFI-
type zeolites with a purely siliceous form (Silicalite-1) are
considered to be potential adsorbents of VOCs.994 However,
the relatively small and sole micropores in conventional
zeolites result in relatively slow mass transport, hindering their
further use in adsorption processes.783 Hierarchically porous
materials are designed and developed to improve their
diffusion performance. Coating or supporting zeolite crystals
on the surface of a permanent porous support to fabricate
hierarchically porous composites (supported zeolites) has been
proven to be an effective method. Yu et al.989 prepared
hierarchically porous diatomite/MFI-type zeolite composites,
which exhibited hierarchical porosity with micropores from the
microporous zeolite and macropores from the macroporous
diatomite support. The prepared composites exhibited higher
benzene adsorption capacity per unit mass of zeolite and less
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mass transfer resistance than microporous Silicalite-1. They
further improved the diffusion performance of diatomite/
zeolite composites by coating desilicated zeolite crystals on the
surface of diatomite.990 The resultant materials exhibited a
special trimodal porosity: macroporosity from the diatomite
support, mesoporosity from desilication treatment, and
microporosity from MFI-type zeolite. Benzene was used as a
model pollutant to evaluate the adsorption performance of the
resulting composites for VOCs. The resultant sample exhibited
a higher adsorption capacity, better affinity, and faster
adsorption kinetics toward benzene than the parent ones.
The improved adsorption capacity was attributed to the
increase in porosity and the formation of terminal silanol
groups on the newly developed pore surface after the
desilication treatment. Kabalan et al.995 investigated the effect
of the morphology (microcrystals, nanocrystals, nanosponges,
and nanosheets) of MFI and BEA type zeolites on their
adsorption capacities of n-hexane at room temperature (Figure
47A−D). The adsorption capacity of n-hexane, which was very
sensitive to the mesopore volume in the adsorbents, was
greatly improved in zeolite nanocrystals or hierarchical
nanoporous materials (nanosheets and nanosponges). The n-
hexane adsorption capacities of hierarchical MFI and BEA
zeolites reached about 790 and 693 mg g−1, which were much
higher than those of microcrystals (130 and 103 mg g−1,
respectively, Figure 47E,F).
4.2.4.2. Catalytic Combustion of Volatile Organic
Compounds. Catalytic combustion is an efficient, econom-
ically feasible, and environmentally friendly technology for the
removal of VOCs. Both noble metals (Pt, Pd, and Au) and
transition metal oxides (Co3O4, FeOx, MnOx, NiO, ZnO, and
CuO) are used as active sites for catalytic combustion of
VOCs. Zeolite-supported noble metal nanoparticles were
reported to exhibit the best catalytic performance for the
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Figure 48. (A) Schematic illustration of the immobilization of lipase enzymes on ZSM-5 zeolites with varying surface and textural properties. (B)
Relationship between enzyme uptake and mesoporous surface area for the immobilization of lipase AK on unmodified and S- or N-functionalized P,
H, HW zeolite-based supports estimated by direct (elemental analysis) and indirect (Bradford) methods. Adapted with permission from ref 998.
Copyright 2011 Elsevier.
combustion of VOCs.996 However, microporous zeolites suffer
from rapid deactivation caused by the poor adsorption and
diffusion of reactant molecules. To accelerate the mass transfer,
Chen and co-workers991,997 synthesized mesoporous Beta and
mesoporous ZSM-5 zeolites and used them as catalytic
supports for toluene combustion. The mesoporous zeolites
displayed a much better catalytic activity than the conventional
ones. Similar results were found in the case of Pt-loaded
hierarchically porous MOR zeolite.992 The materials exhibited
a superior catalytic performance and extraordinary long catalyst
lifetime in toluene combustion when compared with Pt-loaded
microporous zeolites. Wang et al.993 synthesized Ru/
hierarchical ZSM-5 as an efficient bifunctional adsorbent/
catalyst system for the removal of bulky aromatic VOCs. The
value of turnover frequency of the Ru/hierarchical ZSM-5 was
about 2, 3, and 4 times higher than that of Ru/conventional
ZSM-5 toward toluene, o-xylene, and TMB combustion,
respectively, indicating that the Ru/hierarchical ZSM-5 zeolites
had a much better performance in catalyzing the combustion
of bulkier molecules.
4.3. Biological Applications
The capacity of zeolites as carriers for large biological active
species can be improved by introducing meso- or macropores
into the microporous structure. The mesopores thus serve as
hosts for large biological molecules or metal complexes.
Enzymes are one of the most active and selective biocatalysts
used in many chemical reactions. However, the low thermal
stability and poor recycling performances severely limit their
further use in industry. Many efforts have been devoted to
improving the stability and catalytic performance of enzymes
by supporting them on different materials. Materials with
highly accessible surface areas are typically preferred to obtain
high loadings of the catalytic species. Hierarchical zeolites with
large external surface area and tunable surface properties have
received much interest. Mitchell and Pérez-Ramirez ́ 998 studied
the application of hierarchically mesoporous ZSM-5 zeolites as
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carriers for lipase enzymes. Enzymes immobilized on purely
inorganic supports exhibited rapid deactivation due to the
enzyme leaching. The one-dimensional mesopores of the
surface-functionalized MCM-41 resulted in a limited accessi-
bility and a decreased enzyme uptake. In contrast, the
interconnected mesopores in the surface-functionalized hier-
archical zeolites still remained accessible and showed a good
adsorption ability. Lipase immobilized on thiol-functionalized
mesoporous ZSM-5 was also an efficient biocatalyst (Figure
48). Similarly, a hierarchical Zn2+-exchanged ZSM-5/fly ash
cenosphere material was also prepared for separating two
different proteins.999
Moreover, zeolites with a hierarchically porous structure86
and magnetically separable zeolite nanocrystals1000 have been
reported for the separation or immobilization of biomolecules.
The catalysts showed almost the same enzyme-immobilized
capacity and biocatalytic activity when compared with the
microporous zeolites. Besides, they can be easily separated
from the reaction mixture by simple filtration or centrifugation.
Furthermore, the layered zeolite materials provide a large
external surface area for the attachment or entrapment of
enzyme. Hierarchical ITQ-6 zeolite made by the aggregated
nanosheets delaminated from the lamellar precursor of the
ferrierite zeolite was employed as an excellent support for
immobilization of enzymes and was proven to be an efficiently
recyclable enzyme support.1001,1002 The enzymes were
supported on hierarchically structured ITQ-6 zeolites by
covalent bonding, resulting in extremely stable catalysts when
compared with the enzyme in free form and that chemically
bonded to amorphous silica.1002
4.4. Conclusions
Hierarchically porous zeolites have attracted continuously
increasing interests. Different applications of hierarchically
porous zeolites are systematically introduced. Hierarchically
porous zeolites are widely used in catalysis, environmental, and
biological fields due to their large surface area, shortened mass
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diffusion path, improved mass transport, and increased
accessibility for reactants.
Hierarchically porous zeolites can be effectively used in the
catalytic applications. The catalytic reactions with industrial
relevance such as the Friedel−Crafts reaction, the Beckmann
rearrangement, the Fischer−Tropsch synthesis process, the
hydroconversion process, the oxidation reaction, the trans-
formation of methanol, the catalytic cracking reaction, and the
biomass conversion have been chosen to test the catalytic
performance of hierarchically porous zeolites. The hierarchi-
cally porous zeolites exhibited a superior catalytic activity when
compared with microporous zeolites, due to the presence of
meso- or macropores. Besides, the introduced mesopores also
facilitate the escape of coke precursors, thus leading to an
improved resistance to coking.
In addition, hierarchically porous zeolites have long been
utilized for environmental applications. Their multiple pore
sizes leading to reduced diffusion resistance and high surface
areas can be expected to improve their performances in
wastewater treatment, adsorptive desulfurization, CO2 capture,
and removal of volatile organic compounds. Besides, the
diffusion improvement within the hierarchically porous zeolites
can significantly increase their adsorption capacity, especially
when bulky compounds are present.
Hierarchically porous zeolites are also widely used as
biomaterials. Their high external surface area and large pore
volume result in increasing bioactivity and offer more choices
to be functionalized by different groups for novel properties
and improved biocompatibility.
In conclusion, great progress has been made in the field of
hierarchically porous zeolites. The integration of multilevel
porosities into a single zeolite crystal can offer a large surface
area and fast diffusion performance, thus improving the
catalytic performances and adsorption/separation properties
of the catalyst. To improve the properties of the hierarchically
porous zeolite, the hierarchical pore systems should be highly
interconnected, and the introduced meso- or preferably
macropores should be accessible from the outer surface of
the crystal. It is envisioned that many new and exciting
applications of the hierarchically porous zeolites will emerge
owing to the optimization of tunable meso- or macroporous
zeolite structures.
5. CONCLUSION AND FUTURE TRENDS
The field of hierarchically porous zeolites in general has seen
tremendous growth during the past decades. The main
motivation is to reduce the diffusion limitations of molecules
that are imposed by the micropores in the conventional
zeolites. Many new approaches, herein classified as either the
“in situ approach” or “postsynthetic approach”, have been
developed. Most “bottom-up” strategies involve the use of
meso- or macroscale templates, either direct templates, such as
the hard template and soft template, or indirect templates, such
as inert composite partners and active composite partners.
Optimal interactions between the templates and the silicate or
aluminosilicate species in the zeolite synthesis gels are essential
for the success of the “in situ approach”. Different synthesis
methods result in different meso- or macroporosity. Thus, in
order to realize better catalytic performances in zeolites, efforts
should be made to achieve the optimal balance between the
introduced mesoporosity, the intrinsic microporosity, and the
best control of the amount, location, size distribution, and
interconnectivity of the additional pores. In addition, the
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economic and environmental costs should be considered due
to the relatively expensive and irretrievable templates.
Although the “in situ approach” without the use of templates
has been reported, it is still difficult for a large-scale synthesis
due to the time-consuming preparative procedure and the rigid
synthesis condition.
In the “postsynthetic approach”, demetalation was known
for about half a century. The important issue is that not all of
the mesopores are open to the external surface of the zeolite
crystals. Thus, they cannot fully enhance the diffusion through
zeolites. Dealumination was first developed and widely used in
industry. However, the number of acid sites decreased with the
Al-extraction from the framework. The desilication is another
demetalation method to create hierarchical porosity by
dissolving Si in the zeolite framework. Other methods like
the delamination approach lead to the exposure of a larger
fraction of the highly acidic zeolite surface for adsorption and
catalysis. Nevertheless, it can be applied only to a small range
of zeolites. Besides, the high surfactant content and the
alkalinity used for the delamination process result in the partial
dissolution of the zeolite framework. Zeolite recrystallization
through the initial desilication/depolymerization and the
following reassembling process in the presence of conventional
surfactants gives high yield and relatively low environmental
damage when compared with the demetallization, delamina-
tion, and the “in situ approach”. For example, the FCC catalysts
using mesoporous zeolite Y prepared by zeolite recrystalliza-
tion were scaled up and successfully utilized in North
American refineries.381 Although various hierarchical zeolites
can be prepared, the synthesis of hierarchical zeolites with high
structural stability and the design of such multimodal porous
zeolitic materials with a better understanding of the
cooperation between different pore systems still remain great
challenges. Based on the analysis of the function of each pore
system, the hierarchical zeolites with an interconnected micro-
meso-macroporous structure are supposed to be the most
efficient materials. Developing new synthesis strategies to
effectively construct the ideal hierarchical pore architecture
with low economic cost and environmental damage and wide
versatility still remains a great challenge.
Three different types of hierarchically porous zeolites are
distinguished and systematically discussed according to their
different levels of porosity, the micro-mesoporous structured
zeolites, the micro-macroporous structured zeolites, and the
micro-meso-macroporous structured zeolites. Concrete exam-
ples are given to show how to select and to combine different
preparation strategies to fabricate each type of hierarchically
structured zeolite.
In catalytic, environmental, and biological applications,
hierarchically porous zeolites prove to be the most desirable
catalysts/adsorbents/supports. This is due to the introduced
meso- or macropores into the microporous zeolites which can
significantly accelerate the mass transport, reduce the diffusion
path of the reactants, and improve the accessibility of the active
sites, thus leading to an increased performance in certain
applications. Some industrially relevant reactions, such as the
Friedel−Crafts reaction, the Beckmann rearrangement, the
Fischer−Tropsch synthesis process, the hydroconversion
process, the oxidation reaction, the transformation of
methanol, the catalytic cracking reaction, and the biomass
conversion, are selected to evaluate the catalytic performance
of hierarchically porous zeolites. The hierarchical zeolite
catalysts exhibited a superior catalytic activity, selectivity, and
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lifetime when compared with microporous zeolites due to the
improved mass transport and the shortened diffusion path
length. In addition, the multilevel pores in the hierarchically
porous zeolites offer reduced diffusion resistance and high
surface areas for an improved adsorption performance,
especially when bulky compounds are present, in wastewater
treatment, adsorptive desulfurization, CO2 capture, and
removal of volatile organic compounds. Besides, hierarchically
porous zeolites are also widely used in the biological domain
owing to their high surface area and large pore volume which
would improve their bioactive behavior for biological species
and allow them to be loaded with various functional groups to
obtain excellent new functionalities, new properties, and
biocompatibility. The above-mentioned large variety of existing
and promising industrial applications is largely due to the
benefits of a larger additional pore system in the microporous
zeolites. Many new and exciting applications could be found
after creating hierarchically porous zeolites with optimized
properties.
Although a large volume of research is found in the scientific
literature, few reports focus on the establishment of the
quantitative link between the performance and the amount,
location, size, shape, and dimension of each porosity to find the
principles and rules for the design of materials with predictable
properties. The design and preparation of high-performance
hierarchically porous materials still remain quite empirical. We
still follow the “trial−testing−modification−retesting” process
to reach the optimized, but not the best, target materials. Such
a situation is due to the lack of principles, rules, and theories in
the design of advanced materials.
“Learning from nature” could be an important inspiration to
find the concrete examples which serve as rules to follow and
to emulate. The evolution by selection gives various classes of
hierarchically porous organisms, in which pore sizes decrease
along different scales and end in units of constant size, such as
those found in plant stems, leaf veins, and vascular and
respiratory systems. These living hierarchically porous systems
connected within a finite volume can minimize transport
resistance and ensure accelerated transfer over the entire
hierarchical system as a decisive factor for organisms. To
maximize the exchange surface, the living hierarchically porous
networks of organisms have to be evolved with macropores,
expanded by multisized pores with increasing amounts but
decreasing diameters. In 1926, Murray, an American biologist,
established for the first time, on the basis of numerous
examples of living hierarchically porous systems, an empirical
equation referred to as “Murray’s law” with precise diameter
ratios for interconnected multiscale pores from macroscopic to
microscopic levels to quantitatively describe living hierarchi-
cally porous systems of organisms. Indeed, Murray’s law
stipulates the optimized hierarchical design for porous
materials and chemical reactions with maximized transfer
properties. However, since its discovery, Murray’s law has not
received the merit it deserved. Only few works in the design of
chemical reactors based on Murray’s law can be found in the
literature.1003−1005 The main issue is that Murray’s law is only
an empiric description of hierarchically porous systems of
organisms but does not consider the mass variation and
constant surface substance exchange during the mass trans-
portation. Su’s group very recently revisited the Murray’s law
and developed a “generalized Murray’s law” taking the mass
variation and constant surface substance exchange into account
during the mass transportation.10 Such a generalized Murray’s
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law has been used to design and synthesize a series of
bioinspired hierarchically porous materials which emulate the
natural vascular structure whose pore sizes decrease across
macro-meso-micrometer scales and finally terminate in size-
invariant, as in leaves, and blood vascular and respiratory
systems.10 The obtained biomimics enable highly enhanced
mass exchange and transfer in liquid−solid, gas−solid, and
electrochemical reactions and exhibit outstanding properties in
photocatalysis, gas sensing, and Li-ion batteries.10 This first
example of “learning from nature” can serve as a guideline and
lead to further inspiration in the quantitative design and
synthesis of high-performance hierarchically porous materials
with a desirable texture and advanced properties.
Recently, following such a generalized Murray’s law, Su’s
group again successfully synthesized hierarchically mesoporous
ZSM-5 single crystals, containing a micro-mesoporous
structure.674 The hierarchical ZSM-5 materials showed
superior catalytic activity, twice as high as that shown by the
bulky ZSM-5 in the catalytic cracking reaction of isopropyl
benzene owing to its high mass transfer. Besides, this type of
unique ZSM-5 also has outstanding thermal/hydrothermal
stability because of its bioinspired hierarchically porous
structure which leads to homogeneous heat and vapor transfer
and dissipation. A smart moisture-wicking fabric based on
biomimetic micro- and nanofibrous membranes with macro-,
micron-, and submicron-sized pores obeying the “generalized
Murray’s law” by introducing the surface energy gradient has
been prepared. Such biomimetic membranes with multi-
branched pores possessed an excellent moisture-wicking
performance, far superior to the conventional porous
membranes.1006
Based on this, Su and co-workers further demonstrated an in
situ bottom-up confined crystallization process to synthesize a
zeolite ZSM-5 single-crystal reactor (OMMS-ZSM-5)1007 and
zeolite Beta single-crystal reactor (OMMS-Beta)1008 that have
a fully interconnected and highly ordered intracrystalline
macro-meso-microporosity. Such a novel hierarchically porous
structure offering accelerated mass transport and improved
accessibility to active sites can not only increase catalytic
activities and lifetime of OMMS-ZSM-5 in the bulky-molecule
cracking process and methanol-to-olefins reaction1007 but also
greatly enhance catalytic performances of OMMS-Beta in gas-
phase and liquid-phase acid-catalyzed reactions involving bulky
molecules.1008 Most importantly, such a strategy is quite
simple and versatile and has been extended to the synthesis of
other zeolitic materials, including TS-1 and SAPO-34.
Through rational and quantitative design based on this
generalized Murray’s law, the performance of materials can be
significantly ameliorated, and in particular, the bioinspired
hierarchically porous material design based on this generalized
Murray’s law can achieve predictable and optimized functions.
The new era of “material-properties-by-quantitative and real
rational design” based on the “generalized Murray’s law” that
enables the predictable and controlled production of
bioinspired hierarchically porous materials with a quantitative
hierarchy in terms of amount, location, shape, size, and
dimension at every micro-meso-macrometer length scale for
optimized structural features and outstanding performance can
emerge. Hierarchically porous materials with highly enhanced
efficiency, minimum energy, time, and raw material con-
sumption can also revolutionize the design of reactors for a
sustainable life.
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AUTHOR INFORMATION
Corresponding Authors
Li-Hua Chen − State Key Laboratory of Advanced Technology
for Materials Synthesis and Processing, Wuhan University of
Technology, 430070 Wuhan, China; Email: chenlihua@
whut.edu.cn
Weimin Yang − State Key Laboratory of Green Chemical
Engineering and Industrial Catalysis, Shanghai Research
Institute of Petrochemical Technology, SINOPEC, Shanghai
201208, China; Email: yangwm.sshy@sinopec.com
Zaiku Xie − State Key Laboratory of Green Chemical
Engineering and Industrial Catalysis, Shanghai Research
Institute of Petrochemical Technology, SINOPEC, Shanghai
201208, China; Email: xzk@sinopec.com
Bao-Lian Su − State Key Laboratory of Advanced Technology
for Materials Synthesis and Processing, Wuhan University of
Technology, 430070 Wuhan, China; Laboratory of Inorganic
Materials Chemistry, University of Namur, B-5000 Namur,
Belgium; Clare Hall, University of Cambridge, Cambridge CB2
1EW, United Kingdom; orcid.org/0000-0001-8474-0652;
Email: bao-lian.su@unamur.be
Authors
Ming-Hui Sun − State Key Laboratory of Advanced Technology
for Materials Synthesis and Processing, Wuhan University of
Technology, 430070 Wuhan, China; Laboratory of Inorganic
Materials Chemistry, University of Namur, B-5000 Namur,
Belgium
Zhao Wang − State Key Laboratory of Advanced Technology for
Materials Synthesis and Processing, Wuhan University of
Technology, 430070 Wuhan, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.0c00016
Notes
The authors declare no competing financial interest.
Biographies
Li-Hua Chen has been awarded his Ph.D.’s, one in inorganic
chemistry from Jilin University, China (2009), and the other in
inorganic materials chemistry from University of Namur, Belgium
(2011). In 2011−2012, he held a project-researcher position at the
University of Namur with Professor Bao-Lian Su working on
hierarchically porous zeolites. He is currently a full professor working
in the State Key Laboratory of Advanced Technology for Materials
Synthesis and Processing from the Wuhan University of Technology,
China. His research is aimed at new porous materials with designed
hierarchically porosity.
Ming-Hui Sun obtained her B.E. degree at Wuhan University of
Technology (China, 2010) and her Ph.D. at Wuhan University of
Technology (China, 2016) on the design and synthesis of
hierarchically porous zeolite catalysts. She is currently working at
University of Namur (Belgium) in the context of a postdoctoral stay.
Her research focuses on the exploitation and fabrication of novel
porous nanomaterials for catalytic applications.
Zhao Wang received his B.S. degree from Anhui University of Science
and Technology, China, in 2010 and obtained his Ph.D.’s from
Université Pierre et Marie Curie, France, in 2017. In 2018−2019, he
had a postdoctoral fellowship with Professor Bao-Lian Su working on
hierarchically porous materials. He is currently working as an assistant
professor in the State Key Laboratory of Advanced Technology for
BV
pubs.acs.org/CR Review
Materials Synthesis and Processing, Wuhan University of Technology,
China. His research interests mainly focus on porous hierarchy-based
materials, catalysis, and energy conversion.
Weimin Yang, professorate senior engineer, obtained his B.Sc. degree
and Ph.D. in physical chemistry from Nanjing University. He is the
president of SRIPT and the director of the State Key Laboratory of
Green Chemical Engineering and Industrial Catalysis.
Zaiku Xie received his Ph.D. from East China University of Science
and Technology. He was elected academician of the Chinese
Academy of Sciences in 2017. He is now the director of the science
and technology department of SINOPEC and the executive deputy
director of the science and technology committee of SINOPEC. He is
now the vice president of the Catalysis Society of China from 2012,
the vice director of Chinese Chemical Society from 2019, and the
member of the Committee on Chemistry and Industry (COCI) of
IUPAC from 2014. He was elected as a fellow of the Royal Society of
Chemistry in 2013. His research interests focus on the preparation,
characterization, and industrially catalytic conversion of novel zeolite
catalysts.
Bao-Lian Su is a member of the European Academy of Sciences and a
member of the Royal Academy of Belgium, a fellow of the Royal
Society of Chemistry, and a life member of Clare Hall College,
University of Cambridge. He holds “Chaire Francqui au titre Belge”.
He is a full professor and currently the director of the Laboratory of
Inorganic Materials Chemistry (CMI), University of Namur, Belgium.
He is “Strategical Scientist” at the Wuhan University of Technology.
His current research fields include the synthesis, the property study,
and the molecular engineering of organized, hierarchically porous, and
bioinspired materials, biomaterials, living materials, leaflike materials,
and nanostructures and the immobilization of living organisms for
artificial photosynthesis, nanotechnology, biotechnology, cell therapy,
and biomedical applications.
ACKNOWLEDGMENTS
This work is supported by Program for Changjiang Scholars
and Innovative Research Team in University (IRT_15R52) of
the Chinese Ministry of Education. B.-L.S. acknowledges the
Chinese Ministry of Education for a “Changjiang Chaire
Professor” position and a Clare Hall Life Membership,
University of Cambridge. L.-H.C. acknowledges Hubei
Provincial Department of Education for the “Chutian Scholar”
program. This work is also financially supported by NSFC-
21671155, NSFC-U1663225, Major programs of technical
innovation in Hubei (2018AAA012), and Hubei Provincial
Natural Science Foundation (2018CFA054). We thank the
111 Project (Grant B20002) for supporting this work. This
research is also supported by the project “DepollutAir” of
Interreg V France-Wallonie-Vlaanderen.
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