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Synthesis of new zeolite structures

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Cite this: DOI: 10.1039/c5cs00023h

Jiyang Li,a Avelino Cormab and Jihong Yu*a

The search for new zeolites is of continuous interest in the field of zeolite science because of their
widespread application in catalysis and adsorption–separation. To this end, considerable efforts have been
devoted to the preparation of new zeolites with novel porous architectures and compositions. Taking
account of the key factors governing the formation of zeolites (e.g., guest species, framework elements,
construction processes, etc.), several synthetic strategies have been developed recently. These allow the
discovery of many new zeolites with unprecedented structural features, such as hierarchical pores, odd-ring
Received 11th January 2015 numbers (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings), chiral pores, and extremely
DOI: 10.1039/c5cs00023h complex framework topologies, etc. In this review, we will present the advances in the synthesis of new
zeolite structures in the last decade, which are achieved by utilization of the synthetic strategies based on
www.rsc.org/csr pre-designed structure-directing agents, heteroatom substitution, and topotactic transformations.

1. Introduction nucleation is still unknown.4 This makes it difficult to realize

the ‘‘ab initio’’ synthesis of a desired new structure.5,6
Zeolites, as a class of inorganic microporous crystalline materials, Nevertheless, in the last decade, several new synthetic
are widely used in catalysis, adsorption–separation, and ion- strategies have been developed towards the synthesis of zeolites
exchange.1 In addition, new applications of zeolitic materials with specific structures and properties based on the utilization
have also been found in luminescence, electricity, magnetism, of pre-designed organic structure-directing agents,7 heteroatom
medicine, and microelectronics, etc.2 The broad range of zeolite substitution,8 topotactic transformations,9,10 and charge density
applications is a consequence of their specific chemical com- mismatch,11 etc. On the other hand, the advancement of struc-
positions and unique porous structures. Therefore, the search ture determination and computer simulation techniques has
for new zeolites has become a continuous interest in the field of greatly enhanced the researchers’ ability to obtain structure
zeolite science since the pioneering work reported by Barrer in solutions of complex zeolite structures, as well as the prediction
the 1940s.3 In general, zeolite materials are synthesized under of hypothetical zeolite structures. The progress in synthesis and
hydrothermal–solvothermal conditions, and the reaction gel structure determination has led to the rapid developments in
medium contains the framework atoms, solvents, templates or discovering new zeolite framework structures.12 Up to 2007 (the
structure-directing agents (SDAs), and mineralizers. System- sixth edition of Atlas of Zeolite Framework Types), 176 distinct
atization and understanding of zeolite synthesis have been zeolite framework types have been approved by Commission of
tremendous, but the detailed molecular mechanism of zeolite the International Zeolite Association (IZA-SC). To date, the
number of IZA structures has increased to 225,13 while some
new zeolite frameworks have not been approved by IZA-SC yet.
a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Compared to the previously known zeolite framework types,
College of Chemistry, Jilin University, Changchun 130012, P. R. China.
some interesting structural features are found in these newly
E-mail: [email protected]
b
Instituto de Tecnologı́a Quı́mica (UPV-CSIC), Universidad Politécnica de Valencia, discovered zeolites, such as hierarchical pores, odd-ring numbers
Consejo Superior de Investigaciones Cientı́ficas, 46022, Valencia, Spain (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings),

Jiyang Li obtained her PhD degree from Jilin University in 2000, Avelino Corma received his PhD degree from the Universidad
and worked as Humboldt Research Fellow at Göttingen University Complutense de Madrid in 1976. He carried out postdoctoral
(Germany, 2001–2003). Since 2008, she has been a full Professor in research in the Department of chemical engineering at Queen’s
the State Key Laboratory of Inorganic Synthesis and Preparative University (Canada, 1977–1979), and since 1990 he has been
Chemistry, Jilin University. Her research interest is focused on the a research professor at the Instituto de Tecnologı́a Quı́mica
synthesis and properties of novel zeolitic materials. (UPV-CSIC) at the Universidad Politécnica de Valencia. His research
focuses on acid–base and redox catalysis, and zeolite synthesis.

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chiral pores, and extremely complex framework topologies. The quaternary SDAs.15 More specifically, cyclic ketones are reacted
findings of these new zeolites not only enrich the structural with cyclic amines, and then reduced, finally a fourth group is
chemistry of zeolites, but can also enlarge the potential applica- added to the nitrogen to produce charged quaternary SDAs. This
tions of zeolites in catalysis and sorption–separation. procedure allows the synthesis of series of bulky and rigid
In this review, we will focus on the synthesis of new zeolites organic SDAs, resulting in the discovery of new high-silica
during the last decade. Three synthetic strategies that have led zeolites. A notable example is the high-silica zeolite SSZ-57
to the discovery of new zeolites with novel structural features (*SFV) synthesized by using SDA 1 in hydroxide media.16 SSZ-57
will be described: (a) using pre-designed organic SDAs including is the most complex structure known so far, which contains 99
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quaternary and diquaternary SDAs, P-containing SDAs, proton crystallographically distinct T atoms. Its structure has been
sponges, imidazolium derivatives, and metal complexes; (b) using determined by applying the advanced crystallographic tech-
heteroatom substitutions in aluminophosphates, silicates, and niques to high quality single-crystal X-ray diffraction data collected
germanates; (c) using topotactic transformations of 2D–3D, for a microcrystal.17 The idealized structure of SSZ-57 is related to
3D–2D–3D, and 3D–3D structures. Finally, we will present the that of ZSM-11 (MEL) that can be synthesized with the same SDA
challenges and perspectives facing the synthesis of new zeolites in of SSZ-57 in the fluoride media. One of the 16 10-ring channels
the future. in ZSM-11 is replaced by a 12-ring channel in the structure of
SSZ-57, generating the three-dimensional (3D) channel system
composed of intersecting 12-ring, 10-ring, and 10-ring channels
2. Zeolites synthesized by using along the [100], [010], and [100] directions.
pre-designed organic structure- Interestingly, slight changes in SDA 1 lead to different
zeolite structures, indicating the high selectivity between the
directing agents SDAs and zeolite structures obtained (see Table 1).18 Starting
The synthesis of zeolites usually involves the use of alkali metal from SDA 1, changing the butyl group by methyl/ethyl groups
ions or organic amines/ammonium cations as templates or yields aluminosilicate ZSM-12 (MTW) with 1D 12-ring channels.
SDAs. Particularly, the synthesis of high-silica, aluminophosphate, Meanwhile, the use of a cyclo-octyl ring instead of a cyclo-hexyl
and germanosilicate zeolites presents more dependence on the ring in 1 produces another new borosilicate zeolite SSZ-58 (SFG)
use of organic SDAs. A wide range of organic species can be used with 2D 10-ring channels and large cavities. Further attaching a
as SDAs, and these organic SDAs have been recognized as some of methyl group to the pyrrolidine ring produces aluminosilicate
the most important factors to determine the zeolite formation. ZSM-11 (MEL) with 3D 10-ring channels.
Studies show that the pore openings, pore dimensions and their In the case of extra-large pore zeolites, a novel germanoalumino-
connectivities, and pore architectures of the synthesized zeolites silicate zeolite ITQ-43 has been prepared with a hierarchical
can be modified by varying the shape, size, charge, rigidity,
polarity, and hydrophobicity of organic SDAs. Thus, the rational Table 1 SDAs related to N-butyl-N-cyclohexyl-pyrrolidinium (1) and their
design of organic SDAs is one of the most efficient approaches for resulting zeolite structures
the synthesis of novel zeolite structures.7,14 In this section, we will Zeolitic Framework
present some successful examples achieved in the last few years SDA product composition Channel system
by using pre-designed organic SDAs including quaternary and
diquaternary SDAs, P-containing SDAs, proton sponges, imidaz-
SSZ-57
olium derivatives, and metal complexes. Si 3D, 12R  10R  10R
(*SFV)

2.1 Quaternary SDAs

The organic quaternary ammonium cations are commonly used ZSM-11
Si, Al 3D, 10R  10R  10R
SDAs for the preparation of high-silica zeolites. In the past few (MEL)
years, some novel quaternary SDAs have been designed with
the aim of controlling the pore dimensions and synthesizing ZSM-12
Si, Al 1D, 12R
new zeolites. In 2003, Elomari et al. developed a synthetic (MTW)
strategy based on enamine chemistry for the synthesis of novel
ZSM-12
Si, Al 1D, 12R
Jihong Yu received her PhD degree from Jilin University in 1995, (MTW)
and worked as a postdoctoral fellow first at the Hong Kong
University of Science and Technology and then at Tohoku SSZ-58
University (Japan) from 1996–1998. She has been a full Professor Si, B 2D, 10R  10R
(SFG)
in the Chemistry Department, Jilin University, since 1999. She was
awarded the Cheung Kong Professorship in 2007. Her main
research interest is in the rational design and synthesis of nano- ZSM-11
Si, Al 3D, 10R  10R  10R
(MEL)
porous materials.

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mesoporous-microporous structure by using SDA 6.19 The

framework of ITQ-43 has 1D cloverleaf-like 28-ring channels
(21.0 Å  19.6 Å) running along the [001] direction, which are
further connected by 2D 12-ring channels along the [100]
direction (6.8 Å  6.1 Å) and the h110i direction (7.8 Å  5.7 Å).
Later, seven isoindoline-based organic SDAs with increasing sizes
have been designed by Yu and coworkers to systematically study
the synthesis of extra-large pore zeolites.20 As a result, eight
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germanosilicate zeolites have been produced (Fig. 1). Studies

show that the relatively small SDAs or large and very flexible SDAs
yield Beta (*BEA), ITQ-7 (ISV), or ITQ-17 (BEC). Upon increasing
the size of organic SDAs above a certain dimension, extra-large
pore zeolites including ITQ-15 (UTL), ITQ-37 (-ITV), ITQ-44 (IRR),
and ITQ-43 have been obtained.
Fig. 2 Polycyclic quaternary SDAs used in the syntheses of SSZ-52 and
Novel rigid polycyclic SDAs can be generated by using
SSZ-61.
Michael addition reaction. Using this method, a unique poly-
cyclic quaternary SDA 7 has been prepared, which gives rise to a
new aluminosilicate zeolite SSZ-52 (SFW) under high OH/Si Burton and coworkers have designed more flexible quaternary
conditions and in the presence of Al (Fig. 2).21 SSZ-52 is a member ammoniums that have one or more (unfused) ring structures for
of the ABC-6 zeolite family, and its structure features an 18-layer the discovery of new zeolites.23 The reduction of amides (or
stacking of hexagonally arranged 6-rings. The large cavities lactams), enamines, or nitriles is used to prepare the precursor
containing two bulky organic SDAs are found in such a structure, amines. By using this kind of SDA, several zeolites including
which are connected to generate 3D 8-ring channels. Also using SSZ-53 (SFH), SSZ-55 (ATS), SSZ-57 (*SFV), SSZ-58 (SFG), SSZ-59
bulky polycyclic SDA 8, a new high-silica zeolite SSZ-61 (*-SSO) has (SFN), SSZ-60 (SSY), SSZ-63, SSZ-64, and a new zeolite SSZ-65 (SSF)
been produced under relatively dilute conditions using F ions as have been synthesized.
the mineralizer (Fig. 2).22 SSZ-61 possesses dumbbell-shaped
extra-large 18-ring channels. Its framework is closely related to 2.2 Diquaternary SDAs
those of ZSM-12 (MTW) and SSZ-59 (SFN), in which the same The diquaternary ammonium cations composed of rigid rings
layers are found, but their connection modes are different. and flexible methylene chains are a class of feasible SDAs,
which have led to the synthesis of a variety of novel zeolites. For
example, the high-silica zeolites SSZ-74 (-SVR), IM-5 (IMF) and
TNU-9 (TUN) have been synthesized by using diquaternary
SDAs built from N-methyl pyrrolidine heterocycles and the
methylene chains with different lengths (Fig. 3). The structures
of these zeolites are reminiscent of that of MFI, all of them
possess multi-dimensional 10-ring channels. However, their
syntheses are sensitive to the size difference of diquaternary

Fig. 1 Relationship between the different sizes of SDAs and the resulting
products in high-throughput synthesis of germanosilicate zeolites. Reprinted Fig. 3 Varying chain length of diquaternary SDAs leads to different
with permission from ref. 20. Copyright 2008 American Chemical Society. high-silica zeolites.

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SDAs used. SSZ-74 is obtained in the fluoride media with SDA F media.29 Its framework possesses a 3D pore system made of
9,24 which has 3D intersecting 10-ring channels running along intersecting 8-, 10-, and 12-ring channels running along the
the [110], [010], and [001] directions. IM-5 is prepared by using [100], [001], and [100] directions, respectively. With SDA 17, a
SDA 10,25 which features 2D 10-ring channels parallel to a and c, new aluminophosphate zeolite EMM-3 (EZT) containing 1D
respectively. Whereas TNU-9 is synthesized in the presence of SDA 12-ring channels has been synthesized.30
11 and Na+ ions as SDAs,26 whose 3D pore system consists of two In the above cases, the size of the diquaternary SDAs,
parallel 10-ring channels along the [010] direction connected by determined by the length of the methylene chain and the shape

10-ring openings along the [101] direction. Notice that all of these of head groups, obviously affect the size and connection modes
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three zeolites have complex structures containing 24 crystallo- of the resultant channels or cages, resulting in the formation
graphically distinct T sites, which are solved by the combination of different zeolite topologies. Meanwhile, the size of organic
of powder diffraction and electron microscopy techniques. SDAs also influences the amount of negative charges in the
Zones and coworkers designed five different types of diqua- framework, thus affecting the framework compositions. This is
ternary SDAs by varying the heterocycles, and keeping constant important for the synthesis of zeolites with high thermal
the methylene chain lengths of C4, C5, and C6. They systemi- stability (high silica) and strong Brönsted acidity. In addition,
cally study the synthesis in the silica system involving the the linear diquaternary SDAs have more flexibility. A higher
diquaternary SDAs, TMA+/Na+/OH/F ions, and B/Ge/Al hetero- flexibility of the SDA can result in a lower selectivity for a
atoms.27 As listed in Table 2, 18 different zeolite topologies have particular structure but opens up the possibility of synthesizing
been produced by using 15 diquaternary SDAs, and their pore different structures. Indeed, the configuration of the organic
openings vary from small pores (6- and 8-rings), to medium SDAs can be altered according to the different surroundings of
pores (10-rings), and to large pores (12-rings). The size and shape inorganic species, which favours the formation of new zeolite
of heterocycles and the –CH2– chain lengths have an influence structures.
on the resulting zeolite structures. Moreover, the additional In principle, more open structures can be achieved by
inorganic species, such as TMA+/Na+/OH/F and B/Ge, also increasing the size of the organic SDAs. Thus, by using the
control the products formed. large SDA 18 with four chiral centers, a chiral germanosilicate
Recently, a new diquaternary SDA 12 with more heterocycles zeolite ITQ-37 (-ITV) with single gyroidal channels has been
has been synthesized by the reaction of a dihalidealkane (such synthesized (Fig. 4).31 ITQ-37 possesses extra-large 30-ring
as 1,6-dibromobutane) with N-cyclohexylpyrrolidine. This SDA channels, which is the largest in the known zeolites to date.
has led to the discovery of SSZ-82 (SEW) zeolite with a 2D pore Such an open channel system leads to its low framework
system of 10-ring and 12-ring channels.28 density of 10.3 T/1000 Å3. The unique cavities comprising the
Diquaternary SDAs without heterocycles, such as SDA 13–15 enantiomorphous srs nets are found in the framework. The
with different lengths of the methylene chain, can direct the framework and channel systems have the opposite chirality:
synthesis of zeolites ITQ-13 (ITH), ITQ-24 (IWR), and silicate the framework with left-handedness and the channel system
octadecasil (AST). By using SDA 16, a new germanosilicate with right-handedness. Notice that another organic SDA 19 can
zeolite IM-17 (UOV) has been produced in both of OH and also be used for the synthesis of chiral ITQ-37.32
In addition, a new type of unsymmetrical diquaternary
cations has been prepared for the synthesis of zeolites with
Table 2 Five different types of diquaternary SDAs and the resulting zeolite interconnected medium and large pores. As shown in Fig. 5, the
structures
SDA 20 is designed by combination of the rigidity and the
Diquaternary SDA Framework type Pore system flexibility of SDAs used in the syntheses of large-pore (i.e., ZSM-12)
and medium-pore (i.e., ZSM-5) zeolites, respectively. Employing
*BEA 3D, 12R  12R  12R
BEC 3D, 12R  12R  12R the designed SDA 20, a new aluminosilicate zeolite ITQ-39 (*-ITN)
IWW 3D, 12R  10R  8R

MTW 1D, 12R

MOR 1D, 12R
*STO 1D, 12R
SSY 1D, 12R
TUN 3D, 10R  10R  10R
IMF 3D, 10R  10R  10R
-SVR 3D, 10R  10R  10R
MFI 3D, 10R  10R  10R
STI 2D, 10R  8R
STF 1D, 10R
AFX 3D, 8R  8R  8R
RUT 0D, 6R
(n = 4, 5, 6) AST 0D, 6R
NON 0D, 6R
DOH 0D, 6R Fig. 4 Two SDAs used in the synthesis of ITQ-37.

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multipore zeolite ITQ-38 (ITG) with large and medium pores has
been prepared by using a similar diquaternary SDA.35

2.3 Phosphorus-containing organic SDAs

Besides the traditionally used amine and ammonium SDAs, a
new type of phosphorus-containing SDAs has been explored to
synthesize new zeolite structures with large-pore and multi-
dimensional channels. The phosphorus-containing SDAs are
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typically known as phosphonium, phosphazenes, and amino-

phosphine cations. These SDAs are more thermally stable than
the amine/ammonium SDAs and allow more severe crystal-
lization conditions since the Hoffman degradation does not
occur in the synthesis.
As shown in Fig. 6, the validity of using phosphonium
cations as SDAs has been demonstrated in the syntheses of
new zeolites ITQ-26 (IWS),36 ITQ-27 (IWV),37 and ITQ-34 (ITR).38
In the synthesis, F ions are used as a mineralizer and induce
the formation of small cages (such as d4r). Germanosilicate
ITQ-26 (IWS) with a 3D 12-ring large-pore system is synthesized
by using SDA 21.36 SDA 22 is used to synthesize aluminosilicate
ITQ-27 (IWV) with 2D intersecting 12-ring and 14-ring channels.37
Such an SDA is prepared by methylation of diphenylphosphine
with methyl iodide in chloroform in the presence of K2CO3, then
it is changed to the hydroxide salt with an anionic exchange resin.
Fig. 5 Organic SDA designed for the synthesis of ITQ-39 by combination
Notably, the synthesis of ITQ-27 needs relatively long crystal-
of the rigidity and flexibility of SDAs used in the synthesis of ZSM-12 and
ZSM-5, respectively. lization times (59 days).
The prominent directing role of phosphonium SDAs is more
obvious in the synthesis of zeolite ITQ-34 (ITR). ITQ-34 with
has been discovered.33 ITQ-39 exhibits similar disorder to that of connected 9-ring and 10-ring channels has been first discovered
zeolite Beta. Its framework possesses a possible 3D large pore as the polymorph B of the zeolite ITQ-13 (ITH, polymorph A).38
(12-ring) system with available pore opening between those of ITQ-13 can be synthesized by using SDA 23.39 An attempt to
Beta and ZSM-5, or a 3D pore system with large (12-ring) and prepare ITQ-34 with the same SDA only leads to the mixture of
medium (10-ring) intersecting pores.34 As with ITQ-39, a new ITQ-13 and ITQ-34. Several similar SDAs with shorter dicationic

Fig. 6 Phosphonium cations as SDAs used in the syntheses of ITQ-26, ITQ-27, and ITQ-34.

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chains such as ethane-1,2-, propane-1,3-, and butane-1,4-bis- In addition, the aminophosphines containing P–C and P–N
(trimethylammonium) do not favour the synthesis of either bonds that are related to phosphoniums and phosphazenes are
ITQ-13 or ITQ-34, however, their corresponding bis(trimethyl- also found to facilitate the synthesis of novel zeolites, such as
phosphonium) cations 24 and 25 can yield pure ITQ-34. The zeolite STF, ITQ-52, and other unidentified solids. By using SDA
structure-directing role of P-containing SDAs in the formation 27, a silicoborate zeolite ITQ-52 (IFW) has been prepared with
of ITQ-34 has been elucidated by theoretical calculations of the a particularly interesting structure that combines medium
short-range and long-range van der Waals interactions between (10-ring) and small (8-ring) pores (Fig. 7).41
zeolite and SDAs.
2.4 Proton sponges as SDAs
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On the other hand, by using SDA 26 (Fig. 7), a new germano-

silicate zeolite ITQ-49 (IRN) with unusual odd 7-ring units has been Bulky aromatic proton sponges as newly developed organic
prepared in the presence of Ge and F species.40 It is a small-pore SDAs show their advantage in directing extra-large pore zeolites
zeolite containing 8-ring channels and large non-spherical cavities. due to their high basicity along with the large size and rigidity.
Significantly, a new type of SDA based on phosphazenes has Their high basicity makes their protonation in the synthetic
been investigated for the synthesis of zeolites. These SDAs exhibit media, enhancing the inorganic–organic interactions during
several advantages: (1) easy construction by the building-block the nucleation. The large size and rigidity of organic SDAs may
units in a similar way to ‘‘Lego chemistry’’; (2) a large number of offer ‘‘proton sponges’’ with a suitable molecular structure
alkyl groups; (3) adequate polarity and stability; (4) mobilization of for templating extra-large pores. A new extra-large pore silico-
silica or other heteroatoms in the reaction gel through their high aluminophosphate zeolite ITQ-51 (IFO) has been synthesized
basicities; (5) nearly unlimited synthesis flexibility. Such SDAs may with the commercially available SDA 29 (Fig. 9).42 ITQ-51 is
provide more opportunity to direct the formation of particular the first aluminophosphate-based zeolite possessing 16-ring
zeolite structures than quaternary ammonium or phosphonium channels. Importantly, ITQ-51 is stable upon calcination at
SDAs. With this type of SDA 28, ITQ-47 with the BOG topology is 550 1C after the removal of organic SDAs, being a rare example
obtained (Fig. 8). Its framework has Si–B–O composition instead of of hydrothermally stable extra-large pore zeolites. A variety of
Si–Al–O occurring in boggsite that is a rare natural zeolite difficult proton sponge SDAs designed with different sizes, geometries,
to be synthesized. hydrophobicity, or basicity may lead to the discovery of more
new zeolite structures.

2.5 Imidazolium derivatives as SDAs

Imidazolium derivatives as SDAs also promote the discovery of
new zeolite structures. Early work is the zeolites TON, MTT,
MTW, and ITW synthesized by using imidazolium-based SDAs
in basic media or in fluoride media.43,44 Recently, the use of
SDAs 30 and 31 results in the synthesis of germanosilicate
zeolites IM-16 (UOS)45 and IM-20 (UWY)46 (Fig. 10), respectively.
The structure of IM-16 possesses 10-ring channels along the
[100] direction and intersecting 8-ring channels along the [010]
and [001] directions. The 3D channel system of IM-20 is formed
by the intersecting 12-ring channels parallel to the c-axis and
10-ring channels parallel to a-, b- and c-axis.
Silicogermanate zeolite SU-32 (STW) is one of the rare chiral
Fig. 7 P-containing SDAs used in the syntheses of ITQ-49 and ITQ-52. zeolites. Its framework contains helical 10-ring channels run-
ning along the [010] direction and intersected 8-ring channels
running along the [100], [010], and [110] directions. It was first

Fig. 8 Phosphazene SDAs prepared by ‘‘Lego chemistry’’ and the structure

of ITQ-47. Fig. 9 Structure of ITQ-51 zeolite and SDA 29 used in the synthesis.

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Fig. 10 Imidazolium-based SDAs used in the syntheses of IM-16, IM-20, HPM-1, and pure phase and large crystals of NUD-1.

synthesized by using diisopropylamine as an SDA,47 but its low

stability due to the high Ge content (Ge/Si 41) in the frame-
work limits its application. By using imidazolium derivative 32
as an SDA, the first pure silica chiral zeolite HPM-1 with STW
topology has been successfully prepared (Fig. 10).48
Supramolecular self-assembly of aromatic SDAs has proven
to be an effective approach to direct the formation of zeolites.49
This has been demonstrated in the synthesis of ITQ-29 (LTA)
and AlPO4-5 (AFI). More recently, this concept is first applied in
the synthesis of a new extra-large pore germanosilicate zeolite
NUD-1 by using imidazolium-based SDAs.50 The pure phase of
NUD-1 is synthesized by using SDA 33, while the large crystals
of NUD-1 are obtained with SDA 34 (Fig. 10). The extra-large
18-ring channels of NUD-1 are running along the c axis, which
are intersected with the 10-ring and 12-ring channels running
along the a and the b axis, respectively. Although the locations
of SDAs are not determined due to the disorders, the self-
assembled aggregates of SDAs in the structure of NUD-1 are
confirmed by photoluminescent studies of the SDAs in diluted
and concentrated solution, as well as in zeolite NUD-1. Fig. 11 Metal complexes used as SDAs in the syntheses of GaGeO-CJ63
4 3 12 3 2 6
with chiral [3 610 ] cavities and GaGeO-JU64 with chiral [3 4 6 11 ]
2.6 Metal complexes as SDAs cavities.

Metal complexes can be used as SDAs to direct the extra-large

pore or chiral zeolite structures because of their special and cavities are found in its framework, and the racemic [Ni(en)3]2+
rigid conformation. A successful example in the previous work cations are located in the chiral [346103] cavities with the same
is UTD-1 (DON), the first high-silica extra-large pore zeolite handedness, indicating the chirality transfer from the chiral SDA
with 1D 14-ring channels synthesized by using SDA 35 or 36.51 to inorganic framework.
Recently, Yu and coworkers reported a new gallogermanate Later, by using the in situ synthesized chiral SDA 38, another
zeolite GaGeO-CJ63 ( JST) structurally directed by the in situ novel gallogermanate zeolite GaGeO-JU64 ( JSR) has been
formed chiral metal complex 37 in the reaction system synthesized (Fig. 11).53 Its structure contains unprecedented
(Fig. 11).52 GaGeO-CJ63 possesses 3D intersecting 10-ring 3D intersecting odd 11-ring channels running along three
channels running along the [100], [010], and [001] directions. orthogonal directions (Fig. 11). GaGeO-JU64 has the lowest
Its structure is constructed exclusively by 3-rings, resulting in framework density of 9.9 T/1000 Å3 among the known oxide
the low framework density of 10.5 T/1000 Å3. Two unique zeolites to date. The racemic [Ni(1,2-PDA)3]2+ cations induce

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pairs of chiral [3124362116] cavities in the framework of aluminophosphate or aluminosilicate zeolites but with different
GaGeO-JU64. properties. In the past few years, by introducing heteroatoms in
Recently, a series of zeolites with small 8-ring pores, such as the synthesis, many novel zeolites with low-framework density,
Cu-SAPO-34, Cu-SSZ-13, and Cu-SAPO-18, which are important extra-large pores, and chiral pores have been synthesized. In this
catalysts for the selective reduction (SCR) of NOx, have been section, we mainly describe the new zeolites obtained by hetero-
prepared by using Cu amino complexes,54–58 either as the only atom substitution of T sites in aluminophosphates, silicates and
SDAs or in combination with the conventional SDAs. This proce- germanates, as well as of O sites in zeolites.
dure has the advantage of avoiding one step, i.e., the cation
3.1 Heteroatom substitution in aluminophosphates (AlPOs)
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exchange with Cu, during catalyst preparation. The resultant

materials are shown to be highly active and hydrothermally stable. The structure of aluminophosphate (AlPO) zeolites is constructed
Above we have demonstrated that the utilization of novel by the strict alternation of AlO4 and PO4 tetrahedra. The Al and P
pre-designed SDAs allows the synthesis of many new zeolites. atoms in the framework can be easily substituted by heteroatoms
The resulting novel zeolites exhibit unprecedented structural to form MAPO molecular sieves (M = heteroatom). Various
features, such as hierarchical pores, odd ring numbers, extra- elements with different valences can be incorporated into the
large pores, chiral pores, and extremely complex framework MAPO zeolites, such as +1 (Li), +2 (Be, Mg, Ca, Zn, Mn, Fe, Co, Ni,
topology. These unique structures may offer new perspectives Cu, Cd, Sr), +3 (Cr, Co, Fe, Ga, Mo), +4 (Ge, Ti, Sn, Zr, V), and +5
for zeolite materials in catalysis and adsorption–separation. (As, V, Nb).8 The isomorphous substitution of heteroatoms for
The designed SDAs typically possess complex structures of rigid Al/P sites in the framework may generate known AlPO zeolite
rings and flexible chains, and most of them are prepared by analogues. Importantly, in some cases, the heteroatoms may
complex reaction schemes including Diels–Alder, Mannich, stabilize the framework and induce novel zeolite structures. So
Michael addition reactions, which are not commercially avail- far, nearly 30 MAPO zeolites with new topologies have been
able. However, we cannot exclude the opportunity to obtain synthesized (Table 3). All of these new MAPO zeolites cannot be
new zeolites by using commercially available and simple SDAs produced in a similar pure AlPO synthetic system, which high-
as in the cases of the syntheses of zeolites STA-15 (SAF, lights the important role of heteroatoms in the synthesis.
tetrapropylammonium hydroxide), and UZM-5 (UFI, mixture By introducing the divalent metal as a heteroatom, the
of tetramethylammonium and tetraethylammonium). Since a first heteroatom-containing chiral AlPO zeolite MAPO-CJ40
large number of hypothetical zeolite structures have been (M = Co, Zn) with JRY zeotype has been synthesized by Yu
designed and can be predicted to be chemically feasible according and coworkers.60 MAPO-CJ40 crystallizes in the chiral P212121
to the local interatomic distance (LID) criteria,59 in the future, space group. Its framework possesses 1D helical 10-ring
more efforts should be devoted to the design of novel SDAs by channels, which are made of double-helical ribbons with the
systematic modification of the large variety of organic species, same handedness (Fig. 12). Of the three distinct Al sites in the
particular to the ‘‘ab initio’’ design of the organic SDAs towards framework, the heteroatoms occupy the Al (1) position, forming
the synthesis of target hypothetical zeolites. Notice the fact that a helical array along the 10-ring channels. The theoretical study
an SDA might stabilize more than one microporous framework, indicates that the Al (1)-centered tetrahedron has high geo-
other synthetic factors, such as crystallization temperature and metric distortion far from the ideal one. The incorporation of
time, pH, gel concentration and ratios, also influence the zeolite heteroatoms may relax the high distortion, thus stabilizing the
formation. The templating role of SDAs becomes operative only in whole chiral framework.
the gel with right gel chemistry. Also choosing Co and Zn as heteroatoms, two new zeolites
MAPO-CJ62 (JSW) and MAPO-CJ69 (JSN) (M = Co, Zn) with
8-ring channels have been synthesized by using SDA 39 and
3. Zeolites synthesized by using 40, respectively.61,62 In MAPO-CJ62, the heteroatoms are orderly
heteroatom substitution distributed, and selectively occupy two of the three distinct
metal crystallographically positions in the framework, while in
Zeolites are strictly defined as those built up from TO4 tetra- MAPO-CJ69, the heteroatoms occupy the same position with
hedra (T = Si, Al, P). Other elements, such as B, Be, Mg, Ga, Ge, Al atoms in the framework.
Zn, and Co, can isomorphically substitute the zeolite frame- In the presence of Zn as a heteroatom, two new zeolites
work. The introduction of some heteroatoms (except Si, Al, P) in ZnAPO-57 (AFV) and ZnAPO-59 (AVL) have been synthesized by
the zeolite framework may generate special chemical and using SDA 41 and 42, respectively.63 ZnAPO-57 and ZnAPO-59
physical properties, such as catalysis, magnesium, and lumi- represent new members of the ABC-6 family, and both of them
nescence, etc. Moreover, heteroatoms have a great influence on possess a 2D 8-ring pore system. In the synthesis, the addition
the formation of zeolites. For example, heteroatoms Ge, B, Ga, of different heteroatoms including Zn, Mg, and Si, etc., and
Zn, and Be favour the formation of some particular building changing the SDA/H3PO4 ratios may vary the framework charge
units (e.g., 4-rings, 3-rings, d4r, d3r, spiro-5 units, etc.) due to density and yield different zeolite structures. At a high SDA/
their suitable T–O bond and T–O–T angles that can stabilize H3PO4 ratio, the introduction of Si in the synthesis of MAPO-57
these building units. The initial work of heteroatom substitu- or MAPO-59 produces BPH zeolite, while decreasing the
tion is focused on the synthesis of the analogues of known SDA/H3PO4 ratio results in LEV zeolite.

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Table 3 Structures and compositions of new MAPO zeolites without AlPO analoguesa

Type material Framework type code Heteroatom Channel system

ACP-1 ACO Co, Fe 3D, 8R  8R  8R
MAPO-46 AFS Co, Mg, Mn, Ni, Zn, Si 3D, 12R  8R  8R
ZnAlPO-57 AFV Zn, Mg, Si, Zn, Si 2D, 8R  8R
SAPO-56 AFX Mg, Co, Mn, Si, Zr 3D, 8R  8R  8R
CoAPO-50 AFY Co, Zn, Mg, Mn 3D, 12R  8R  8R
ZnAlPO-59 AVL Zn, Mg, Si, Zn 2D, 8R  8R
Beryllophosphate-H BPH Mg, Zn, Si 3D, 12R  8R  8R
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DAF-1 DFO Co, Mg, Ni 3D, 12R  10R  8R

DAF-2 DFT Co 3D, 8R  8R  8R
Edingtonite EDI Co, Cu 3D, 8R  8R  8R
Faujasite FAU Co, Cu, Zn, Si 3D, 12R  12R  12R
CoAPO-CJ40 JRY Co, Zn, Mn, Fe 1D, 10R
CoAPO-CJ69 JSN Co, Zn 2D, 8R  8R
CoAPO-CJ62 JSW Co, Zn 1D, 8R
Laumontite LAU Co, Zn, Mn, Fe, 1D, 10R
Merlinoite MER Co 3D, 8R  8R  8R
UiO-28 OWE Co, Mg 2D, 8R  8R
Phillipsite PHI Co, Zn 3D, 8R  8R  8R
Rho RHO Co, Mn, Mg 3D, 8R  8R  8R
STA-1 SAO Zn, Mg 3D, 12R  12R  12R
STA-6 SAS Mg, Mn, Fe, Zn, Co 1D, 8R
STA-2 SAT Mg 3D, 8R  8R  8R
Mg-STA-7 SAV Co, Zn, Mg, Mn, Fe 3D, 8R  8R  8R
UCSB-8Co SBE Co, Zn, Mg, Mn 2D, 12R  8R
UCSB-6GaCo SBS Co, Zn, Mg, Mn 3D, 12R  12R  12R
USCB-10GaZn SBT Co, Zn, Mg 3D, 12R  12R  12R
SIZ-7 SIV Co 3D, 8R  8R  8R
Thomsonite THO Co 3D, 8R  8R  8R
a
Updated based on Table 1 in ref. 8.

with high stress. Thus incorporation of heteroatoms in silicates

may introduce the possibility of generating new zeolite structures.
The incorporation of Ge atoms into the silicate zeolites has
been shown by Corma and coworkers to favour the formation of
d4r and d3r cages, thus leading to novel zeolite structures with
low framework density, extra-large pore, and unprecedented
pore opening, etc. A series of germanosilicate zeolites ITQ-n
have been discovered coupled with the use of pre-designed
organic SDAs in OH and F in concentrated gels (Table 4). All
of these zeolite structures exclusively contain d4r cages that are

Table 4 Structural features of germanosilicate ITQ-n zeolitesa

Zeolite Building Si/Ge

Fig. 12 Framework structure of CoAPO-CJ40 viewed along the [010] Zeolite type units ratio Channel system
direction, and the distribution of Co (blue) atoms in helical 10-ring
channels. ITQ-15 UTL d4r 10 2D, 14R  12R
ITQ-17 BEC d4r 2 3D, 12R  12R  12R
ITQ-21 — d4r 20 3D, 12R  12R  12R
ITQ-22 IWW d4r 20 3D, 12R  10R  8R
3.2 Heteroatom substitution in silicates and germanates ITQ-24 IWR d4r 5 3D, 12R  10R  10R
ITQ-26 IWS d4r 4 3D, 12R  12R  12R
A theoretical study by Brunner and Meier shows that zeolites ITQ-29 LTA d4r 2 3D, 8R  8R  8R
ITQ-33 ITT d4r 2 3D, 18R  10R  10R
with low framework density and large micropore volumes could
ITQ-34 ITR d4r 10 3D, 10R  10R  9R
be preferentially formed by small 3-rings and 4-rings.12 It is ITQ-37 -ITV d4r 1 3D, 30R  30R  30R
known that the T–O bond lengths, especially the T–O–T bond ITQ-38 ITG d4r 4.5 3D, 12R  10R  10R
ITQ-40 -IRY d4r, d3r 1 3D, 16R  16R  15R
angles will affect the formation of these small rings. In the
ITQ-43 — d4r 2.2 3D, 28R  12R  12R
silicate zeolites, 3-rings and 4-rings are less stable than 5-rings ITQ-44 IRR d4r, d3r 2 3D, 18R  12R  12R
or 6-rings. Compared to the Si–O–Si bond angle, those of ITQ-49 IRN d4r 4.7 1D, 8R
ITQ-54 — d4r 1 3D, 20R  14R  12R
Si–O–Ge, Ge–O–Ge, Si–O–Al, and Si–O–B may vary in a relatively
a
small range, which is beneficial for the formation of small rings Updated based on the Table 4 in ref. 5.

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Other heteroatoms, such as Zn, Ga, B, Be, Li, etc., can also be
incorporated into the zeolite frameworks to form new zeolite
structures. Notable examples are zinc-based silicate VPI-9
(VNI),69 gallium-containing silicates TsG-1 (CGS)70 and ECR-
34 (ETR),71 borosilicate zeolites SSZ-58 (SFG),72 SSZ-53 (SFH),73
SSZ-60 (SSY),74 and ITQ-52 (IFW),41 beryllosilicate zeolite LSJ-10
(JOZ),75 and Li-containing zeolites MFI,76 ANA,77 RUB-23,78 and
RUB-29,79 etc. ECR-34 is a new gallosilicate zeolite, which
possesses 1D extra-large 18-ring channels along the c-axis.71
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Notice that no aluminosilicate or silicate analogue of ECR-34

Fig. 13 Framework structures of ITQ-40 and ITQ-44 containing d3r and has been found yet. ITQ-52 is synthesized with the organo-
d4r cages. phosphorus SDA in the presence of B species.41 It presents
interconnected small and medium pore systems. The as-made
ITQ-52 with a Si/B ratio of 17.2 is stable, and most of the B
stabilized by the framework Ge atoms and/or the occluded F atoms remain in the framework after the removal of organic
ions. Interestingly, unusual d3r cages have been first observed SDAs upon calcination or thermal treatment under diluted H2.
in the germanosilicate zeolite ITQ-40 (-IRY).64 ITQ-40 contains a LSJ-10 (JOZ) exhibits the typical framework of beryllosilicate,
large 3D channel system and has a low framework-density of which features the spiro 5-rings centered on BeO4 tetrahedra
10.1 T/1000 Å3 (Fig. 13). In its framework, 15-ring channels are cross-linked by 4- and 5-rings formed from SiO4 tetrahedra
running along the [001] direction, which connect to the 2D (Fig. 14).75 It contains 3D 8-ring channels running along a, b,
16-ring channels running along the h100i directions. The small and c axes. LSJ-10 shows high-temperature stability, and its
T–O–T angles (o1301) in d3r cages are relaxed by Ge atoms. framework remains integrated to 750 1C before starting to
Besides Ge atoms, Al and B heteroatoms can also be introduced recrystallize, which may be related to the small pore structure
into the framework of ITQ-40. and strength of the short Be–O and Si–O bonds.
Another silicogermanate zeolite ITQ-44 (IRR) containing d3r The incorporation of B, Al, and Ga atoms into the germanate
cages has been synthesized with the directing effect of rigid and frameworks has also been made to synthesize novel zeolite
bulky SDA 43 and the Ge atoms (Fig. 13).65 ITQ-44 is the first structures. The feasibility of this method is demonstrated by
zeolite possessing a 3D pore system made of intersecting 18- the synthesis of SU-16 (SOS), a boron-containing germanate
and 12-ring channels. In its framework, Ge atoms preferentially zeolite (Ge/B ratio = 2), under hydrothermal conditions by using
occupy the d3r cages (50% occupancy of Ge), then occupy the SDA 44.80 The framework of SU-16 features 3-rings (B2Ge) and
d4r cages (37% occupancy of Ge), indicating the important role 4-rings (BGe3). It possesses a 3D intersecting channel system, in
of Ge atoms in stabilizing the small d3r and d4r cages. which three 8-ring channels and three 12 ring channels are

On the other hand, the unprecedented pore openings have perpendicularly intersected along the [010], [011], and [011]
also been found in germanosilicate zeolites. ITQ-43 is the first directions.
hierarchical crystalline zeolite containing 12-ring micropores A spiro-5 unit composed of two corner-sharing 3-rings has
and 28-ring mesopores in the framework;19 PKU-16 (POS) is high inner tension, which is relatively rare in zeolite structures
the first germanosilicate zeolite with a 3D channel system of although a few germanate zeolites containing 3-rings have
11-rings, 11-rings, and 12-rings;66 and ITQ-54 is a multi- been found. By introducing the Al atom in germanates, a new
dimensional extra-large zeolite with 20-ring, 14-ring, and aluminogermanate zeolite PKU-9 (PUN) containing spiro-5
12-ring pores.67 units has been hydrothermally synthesized (Fig. 14).81 The
In the reported germanosilicate zeolites, the Si/Ge ratio in framework of PKU-9 contains wrinkled CGS layers connected
the framework varies from 1 to 20. A high content of Ge atoms
in the framework may result in a low thermal stability of the
product unless the framework density is larger. To meet the
practical applications of the germanosilicate zeolites, many
attempts have been made to decrease the Ge amount in the
framework, and enhance the hydrothermal and thermal stabi-
lity of the resulting materials. For example, a post synthetic
treatment by degradation of zeolite structures through removing
Ge-containing d4rs, replacing Ge by Si atoms in the framework,
post-synthetic isomorphous substitution of Al for Ge, or trans-
formation of the as-synthesized silicogermanate into high-silica
zeolitic sheets or related zeolites have been used.9,10,68 In other
way, the suitable SDAs can be designed to better stabilize the
structure, thus decreasing the Ge contents in the framework as Fig. 14 Framework structures of LSJ-10 and PKU-9 containing spiro-5
in the case of pure silica zeolite HPM-1 (STW).48 units.

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by spiro-5 units, which possess 3D channel systems composed containing zeolites with a high degree of substitution, the

of 10-ring channels running along the [001], [110], and [110] incorporated heteroatoms may change the T–O bond lengths
directions, and the interconnected 8-ring channels along the and T–O–T bond angles of TO4 tetrahedra in the framework,
[001] direction. Al and Ge atoms are randomly distributed in thereby, stabilizing the formation of novel zeolite structures
the framework of PKU-9 with the occupancy of 0.22 and 0.79, with specific building units. In the latter case, the existence of
respectively. In each spiro-5 unit, the two corner-shared 3-rings heteroatom is essential for the synthesis of the specific zeolite
are perpendicularly arranged, resulting in the significantly structures, in which the heteroatoms may preferentially occupy
smaller T–O–T angles (123.8–128.91). The existence of Al atoms the special positions in the framework. Notice that a high
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may decrease the inner tension of the spiro-5 unit, thus amount of metal heteroatoms in the framework may decrease
stabilizing the framework structure. the thermal stability of the zeolite. It is important to substitute
heteroatoms by Si and/or Al through direct or post-synthesis for
3.3 Heteroatom substitution of oxygen atoms in zeolites their practical applications.

The frameworks of classical zeolites are based on oxide-sharing

tetrahedra. The substitution of oxygen by nitrogen in the zeolite
frameworks has opened up a new way to synthesize novel 4. Zeolites synthesized by topotactic
zeolite structures that are not feasible as oxides. Nitrido- transformation
zeolites are of great interest due to their special chemical and
physical properties, such as higher thermal stability and adjust- Different from the traditional synthesis of zeolites under hydro-
able acidity/basicity. Moreover, nitrogen atoms as three-bridging thermal or solvothermal conditions, the topotactic transformation
atoms are commonly found in the framework, and the smaller of zeolite frameworks has been developed as an effective method
T–X–T (X = N, O) angles may generate rare 3-rings as well as large for the synthesis of new zeolite materials. The topotactic trans-
rings, forming novel zeolite topologies. Several nitrido-zeolites formation of zeolites can be defined as a solid-state structural
have been prepared, such as nitridosodalites (SOD),82 related transformation from one precursor into another structure through
oxonitridosodalites (SOD),83 and nitridophosphate-1 (NPO).84 a series of treatments, such as dehydration–condensation, inter-
Recently, an oxonitridophosphate Ba19P36O6+xN66xCl8+x calation–condensation, degradation–condensation, disassembly–
(x E 4.54) (NPT) with novel zeolite topology has been synthe- reassembly, and phase-to-phase reconstruction. This method can
sized by heating a reaction mixture of phosphoryl triamide, be used to prepare some new zeolite structures with predetermined
thiophosphoryl triamide, BaS, and NH4Cl at 750 1C.85 Its layers, cages, and pores. In this section, we will describe the new
framework is composed of P(O, N)4 tetrahedra to form a novel zeolite structures prepared through the 2D–3D transformation,
3846812 cage. Such cages are further connected to build the 3D–2D–3D transformation, and 3D–3D transformation.
framework containing a 3D 8-ring channel system (Fig. 15). The
framework of NPT has a very high thermal stability up to at 4.1 2D–3D transformation
least 1100 1C. Most of the 2D–3D transformation is the topotactic condensa-
Above we have demonstrated the role of heteroatom sub- tion of the layered precursors into 3D structures by solid-state
stitution in directing and stabilizing new zeolite structures. In reaction with thermal treatment. This is a dehydration–
some heteroatom-containing zeolites with a low degree of condensation process, in which the silanol groups on the
substitution, the heteroatoms are randomly distributed in the surface of two neighboring layers dehydrate and condensate
framework, which may change the framework charge density, spontaneously, forming high-silica zeolites while keeping the
but not the framework topology; while in some heteroatom- layered structures. In this case, the layer precursor should have
the proper number and intra-layer distance of terminal silanol/
siloxy groups on either side of the layer, as well as suitable
organic SDAs with low charge density.86 Such a process always
leads to guest free materials, which is of particular importance
for small pore materials e.g. silica sodalite. Also, the platy
morphology of the precursor can be maintained.
Early in 1988, Lowe and coworkers reported the synthesis of
a thermally stable silica polymorph EU-20 (CAS/NSI) converted
from piperazine silicate EU-19.87 However, the condensation of
EU-19 was only proposed conceptually due to the unclear
structure of EU-20. In 1994, boron aluminosilicate zeolite
MCM-22 (MWW) represented the first example of 2D–3D zeolite
transformation, which was synthesized by a layered precursor
MCM-22P.88 Since then, several high-silica zeolites have been
prepared by such topotactic conversion of layered silicates
Fig. 15 Framework structure of NPT connected by 3846812 cages. (Table 5). Particularly, four new zeolite topologies including

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Table 5 Zeolites synthesized by topotactic condensation of layered

structures

Type material Framework type Precursor

EU-20 CAS EU-19
MCM-22 MWW MCM-22-precursor
RUB-41 RRO RUB-39
RUB-24 RWR R-RUB-18
Zeolite RWR RWR AA-RUB-18
CDS-1 CDO PLS-1
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RUB-37 CDO RUB-36, RUB-38, RUB-48

MCM-65a CDO MCM-65b
UZM-25 CDO UZM-13, UZM-17, UZM-19
Unnamed CDO Several unnamed
Unnamed CDO PLS-4
RUB-15-SOD SOD HOAc-RUB-15
Silica-sodalite SOD HAc-RUB-15
CDS-3 FER PLS-3
Ferrierite FER PREFER
ERS-12a Incomplete condensation ERS-12b
Fig. 16 Post-synthesis of interlayer expanded zeolites through dialkoxy-
MCM-47a MCM-47b
ERB-1a MWW ERB-1 silylation of a lamellar precursor (e.g., MWW precursor): (a) MWW lamellar
ITQ-1a MWW ITQ-1b precursor; (b) interlayer expanded via the reaction of silane and silanols; (c) a
Nu-6(2) NSI Nu-6(1) novel 3D structure with an expanded pore window after calcination,
EU-20b CAS EU-19 (d) common 3D MWW structure obtained through direct calcination. Reprinted
IPC-4 PCR IPC-1P with permission from ref. 94. Copyright 2008 American Chemical Society.
a b
The type material is calcined. The precursor is synthesized without
calcination.
Interestingly, an alternative 2D–3D topotactic transforma-
tion has been presented by Wu and coworkers by incorporating
CDO, NSI, RRO, and RWR have been discovered, which cannot Si between layers before condensation.94 Different from the
be obtained by direct hydrothermal synthesis so far. direct topotactic condensation from layer precursors that
A silicate zeolite CDS-1 (CDO) has been synthesized by generate zeolites with 8-ring or 10-ring pores, such a method
dehydration–condensation of layered silicate PLS-1 heated may lead to new zeolite structures with more open pores. In
at high temperature under vacuum.89,90 The sheets of PLS-1 their work, one-step post-alkoxysilylation with diethoxydi-
are condensed and polymerized along the [100] direction by methylsilane has been realized on the zeolitic lamellar precur-
dehydration to generate CDS-1, and TMAOH molecules located sors including MWW, FER, CDO, and MCM-47. The new
between the layers are removed. The framework of CDS-1 exhibits expanded zeolite structures with larger pore windows, high
a novel zeolite topology, which has straight 8-ring channels along crystallinity, and excellent hydrothermal stability have been
the [010] and [001] directions. The structure of the PLS layer is well obtained by calcination of these post-treated lamellar precursors
maintained in the framework of CDS-1. Other than PLS-1, several to remove the organic moieties (Fig. 16). The interlayer-expanded
layer structures including RUB-36, RUB-38, RUB-48, UZM-13, zeolite based on MWW precursor exhibits higher catalytic activi-
UZM-17, UZM-19, PSL-4, and MCM-65 have also been used as ties in the redox and solid acid-catalyzed reactions of bulky
precursors to prepare CDO-type zeolite structures. molecules than the conventional MWW zeolite. Similar inter-
Zanardi et al. have studied the transformation of Nu-6(1) and layer expansion of the layered zeolite precursors RUB-39 and
Nu-6(2) (NSI), and elucidated their structures using an integrated RUB-36 can yield the new microporous frameworks COE-1/COE-2,
approach based on experiments and model building.91 The penta- and COE-3/COE-4, respectively.95,96 In addition, a new class of
sil layer structure of Nu-6(1) is similar to previously recognized zeolite Lewis acid catalysts can be derived from the layered zeolite
EU-19 and MCM-69, but the SDA of 4,4’-bipyridyne used in the precursor RUB-36 by using Fe salt instead of a silylating agent in
synthesis results in the different symmetry and stacking para- the interlayer expansion reaction.97
meter. The layers of Nu-61 parallel to the (100) plane condense to In the 2D–3D topotactic transformation, the different condensa-
form a 3D framework of Nu-6(2) with a novel zeolite topology, in tions of the same layer may give rise to different zeolite structures.
which two types of 8-ring channels are found along the b direction. For example, the fer layers with an ABAB stacking sequence along
By calcination of a layered silicate RUB-39 at 600 1C, a new the a-axis generate zeolites FER and CDO due to the different shift
high-silica zeolite RUB-41 (RRO) with small to medium pores vector. As for the cas layers, the condensation of cas layers with
has been obtained.92 The framework of RUB-41 possesses a 2D ABAB and AAAA stacking sequences results in CAS and NSI zeolite,
channel system with intersecting 8-ring and 10-ring channels respectively. Layers A and B are the mirror image of each other.86
running along the [001] and [100] directions, respectively.
In addition, a new small pore zeolite RUB-24 (RWR) with 1D 4.2 3D–2D–3D transformation
straight 8-ring channels has also been prepared by topotactic Contrast to the 2D–3D topotactic condensation, the 3D–2D–3D
condensation of intercalated silicate layer precursor R-RUB-18 framework conversion is also a feasible approach to generate
(R = alkylammonium cations) in air at 500 1C.93 new zeolite structures. The frameworks of some germanosilicate

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zeolites are made of 2D layers connected by d4r units. Considering

that the Ge atoms usually preferentially occupy the d4rs, and the
bond between the layers and d4rs is easy to hydrolyse in the
presence of water, the 3D–2D conversion can be achieved by
degradation of interlayer d4r connectors. The resulting 2D layers
are further condensed by calcination to form a novel 3D zeolite
structure. This topotactic condensation can decrease the Ge con-
tents in the framework, as well as synthesize new zeolite structures.
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A successful example of 3D–2D–3D transformation is pre-

sented by Cĕjka and coworkers.98 In detail, the calcined UTL
zeolite as a precursor is treated hydrothermally from room
temperature to 100 1C and the pH range is adjusted from neutral
to acidic (0.1 M HCl). The d4r units are removed from the
structure, resulting in the transformation of the 3D structure into
the 2D lamellar layer (denoted IPC-1P). Then, the new IPC-1P
layers are further modified with a silylating agent in the nitric acid Fig. 17 Suggested pathway from ITQ-29 to ITQ-50. (a to b) Reversible
solution, and generating new germanosilicate zeolite IPC-2 (OKO) deformation; (b to c) Si–O bond breaking and formation through displace-
ment of O atoms; (c to d) structure relaxation. Reprinted with permission
after calcination. Another example of 3D–2D–3D conversion is from ref. 102. Copyright 2013 Wiley-VCH.
achieved by Kirschhock and coworkers in the transformation
of IM-12 (UTL) zeolite into a new Ge-free zeolite COK-14
(OKO).99 Ge-containing d4r units in the germanosilicate IM-12 to ify cages, half of the d4r cages remain and the others convert to
can be removed in strong mineral acid. By leaching and calcina- sti units through the breakage of one edge of d4r cages, and the sod
tion of the products, the new all-silica zeolite COK-14 with an cages are kept. As a result, ITQ-50 possesses 2D interconnected
intersecting 12- and 10-ring channel system is prepared. 8-ring channels along the [001] and [110] directions. Fig. 17 shows
Remarkably, a top-down method has been developed by the transformation of lta cages into ify cages through three
Cĕjka and coworkers, which involves the disassembly of a structural modifications.
parent zeolite into its constituent layers followed by their To date, new zeolites obtained through the topotactic trans-
reassembly into new zeolites with targeted topologies.100 The formation have been relatively rare. Synthesis of novel and
idea of this method is tailoring the linkers used in the reas- thermally stable layered zeolite precursors by the direct syn-
sembly, and further to control the generated structures with thesis or post-synthesis treatments is the key for this strategy.
predetermined pore sizes. Two new zeolites IPC-4 (PCR) and In addition, exploitation of more feasible methods to achieve
IPC-2 (OKO) have been synthesized by using this strategy from a the effective topotactic transformation, as well as the under-
parent zeolite UTL with 12-ring and 14-ring channels. The standing of their transformation mechanisms may allow us to
replacement of d4rs in UTL by 4-rings or oxygen atoms results prepare many more novel zeolite structures.
in IPC-2 with smaller 12  10 ring channels and IPC-4 with even
smaller 10  8 ring channels, respectively. Note that there is no 5. Summary and perspectives
direct synthesis route available yet for IPC-2 and IPC-4 zeolites.
Recently, the mechanism of the disassembly and reassembly The number of new zeolite structures has been rapidly growing
of the layered silicate precursor RUB-36 to FER-type zeolite has in the last decade. Since porous materials are involved in
been studied.101 This opens up new vistas for the synthesis of various processes of current interest, energy saving catalytic
new zeolite structures through topotactic transformations. processes, environmentally benign sorbents, storage materials
for waste and energy etc., in general, there is potential in every
4.3 3D–3D reconstructive transformation new material synthesized. In this review, we have demonstrated
More recently, an interesting 3D–3D reconstructive transformation the recent progress achieved in the synthesis of new zeolite
of zeolite through the effect of pressure has been shown, and a structures by applying the three main synthetic strategies based
new zeolite ITQ-50 (IFY) was produced from the pure silica zeolite on pre-designed organic SDAs, heteroatom substitution, and
ITQ-29 (LTA).102 ITQ-29 undergoes two structural transformations topotactic transformation. Utilization of pre-designed organic
under pressure. A reversible transformation occurs at 1.2 GPa and SDAs allows the synthesis of new zeolites with hierarchical
ITQ-29 is recovered after pressure release. Moreover, an order-to- pores, odd-rings, extra-large pores, and extremely complex
order reconstructive phase transition occurs at approximately framework topologies, etc.; utilization of heteroatom substitu-
3.2 GPa, leading to a new crystalline zeolite ITQ-50 (IFY) that is tion allows the synthesis of new zeolites with low framework
non-reversible upon pressure release. The structures of ITQ-29 and density, extra-large pores, chiral pores, and special building
ITQ-50 are quite different although some of their building units units (d3r, d4r, 3-rings, 4-rings, etc.); utilization of topotactic
are related. The framework of ITQ-29 is composed of three transformation allows the synthesis of new zeolites with pre-
composite building units (CBUs) including lta, sod, and d4r. determined layers, pores, and cages. The discovery of these new
During the phase transition of ITQ-29 to ITQ-50, lta cages change zeolites with unprecedented structural features may offer new

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perspectives for zeolite materials in applications in catalysis 7 (1S,6S)-2,2-Diethyl-6,7-dimethyl-2-azoniabicyclo[3.2.2]-

and adsorption–separation. nonane;
Despite the synthesis progress made, several challenges 8 18-Azonia-8,8-diethyltetracyclo[4.3.3.12,5.01,6]tridec-3-ene;
remain in the synthesis of new zeolite materials. The first one 9 1,1 0 -(Hexane-1,6-diyl)bis(1-methylpyrrolidinium);
is the synthesis of zeolites with extra-large pores/cavities and 10 1 0 -(Pentane-1,5-diyl)bis(1-methylpyrrolidinium);
high thermal stability for the application in catalysis of heavy 11 1,1 0 -(Butane-1,4-diyl)bis(1-methylpyrrolidinium);
oils. This needs the design of novel SDAs (e.g., bulky and rigid 12 1,6-Bis(N-cyclohexylpyrrolidinium)hexane;
SDAs, supramolecular organic SDAs, etc.) and increasing the Si 13 N1,N1,N1,N3,N3,N3-Hexamethylpropane-1,3-diaminium;
N1,N1,N1,N4,N4,N4-Hexamethylbutane-1,4-diaminium;
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contents in the framework. Second is the discovery of new 14

zeolites with special pore rings, such as 11-, 13-, 15-, 17-, and 15 N1,N1,N1,N5,N5,N5-Hexamethylpentane-1,5-diaminium;
19-rings, which could be useful for shape-selective catalysis. For 16 Decamethonium;
doing this it is possible to theoretically predict such zeolite 17 N1,N1,N1,N6,N6,N6-Hexamethylhexane-1,6-diaminium;
structures, and then design organic SDAs and select framework 18 N,N,N0 ,N0 -Tetraethyl-1,8-dimethyl-bicyclo-exo,exo-[2.2.2]oct-
cations to direct their synthesis. Third is the synthesis of a single 7-ene-2,3:5,6-dipyrrolidinium;
enantiomer of a chiral zeolite for the applications in asymmetric 19 30 ,40 -Dihydro-10 H-spiro[isoindoline-2,20 -isoquinolin]-2-ium;
catalysis and separations. For this purpose, efforts should be 20 1,1-Dipropyl-4-(1-propylpyrrolidinium-1-yl)piperidinium;
devoted to the following aspects: (1) selecting suitable frame- 21 (1,3-Phenylenebis(methylene))bis(triethylphosphonium);
work atoms to favour the formation of a chiral framework; 22 Dimethyldiphenylphosphonium;
(2) using chiral SDAs (e.g., metal complexes) to direct the chiral 23 Hexane-1,6-bis(trimethylammonium);
structure units and further organize the chiral framework; 24 Propane-1,3-diylbis(trimethylphosphonium);
(3) attaching the chiral molecules or groups (e.g., chiral organo- 25 Propane-1,3-diylbis(trimethylphosphonium);
silane) to the inorganic framework through covalent bonds 26 Butane-1,4-diylbis(tri-tert-butylphosphonium);
during the nucleation process to generate chiral structures. 27 3,3,8,8-Tetrakis(dimethylamino)-2,9-dimethyl-2,9-diaza-
Currently, the rapidly developed computation techniques play 3,8-diphosphoniadecane-3,8-diium;
an important role in the prediction of hypothetical zeolite 28 tert-Butyl-iminotris(dimethylamino)phosphorane;
structures.12 A large number of hypothetical zeolites with desired 29 1,8-Bis(dimethylamino)naphthalene;
pore architectures have been designed.103,104 Towards the 30 1-Ethyl-3-methyl-1H-imidazol-3-ium;
rational synthesis of target hypothetical zeolites,5,6 the suitable 31 1-Butyl-3-methyl-1H-imidazol-3-ium;
SDA candidates should be predicted by using the computational 32 2-Ethyl-1,3,4-trimethyl-1H-imidazol-3-ium;
modeling or the ‘‘ab initio’’ design, followed by the proper selection 33 1-Methyl-3-(4-methylbenzyl)-1H-imidazol-3-ium;
of the framework cations based on their structural features. Data 34 1-Methyl-3-(naphthalen-2-ylmethyl)-1H-imidazol-3-ium;
mining techniques and various synthetic approaches (particularly 35 Bis(tetramethylcyclopentadienyl)cobalt(III);
high throughput techniques) will greatly guide their synthesis by 36 Bis(pentamethylcyclopentadienyl)cobalt(III);
predicting the synthesis conditions and fast-screening the experi- 37 [Ni(en)3]2+ (en = ethylenediamine);
ments. The computational chemistry has become a very important 38 [Ni(1,2-PDA)3]2+ (1,2-PDA = 1,2-diaminopropane);
tool in assisting the discovery of new zeolites. It is worth noting 39 N-Methylpiperazine;
that a deep understanding of the formation mechanism at the 40 Diethylamine;
molecular level is essential for the rationalization of zeolite syn- 41 Diethyldimethylammonium;
thesis. Moreover, the spirit of the chemists is the driving force 42 Ethyltrimethylammonium;
leading us to promoting the development of zeolite science in the 43 (20 -(R),6 0 -(S))-2 0 ,6 0 -Dimethylspiro[isoindole-2,10 -piperidin-
near future. We hope that this view will stimulate more advances 1 0 -ium];
in the synthesis of new zeolites with predetermined structures and 44 Diethylenetriamine
functions.

Acknowledgements
Abbreviations We thank the State Basic Research Project of China (Grant no.
2011CB808703 and 2014CB931802) and the National Natural
The full names for SDAs (only one name is given for a
Science Foundation of China (Grant no. 21271081, 91122029
complicated SDA):
and 21320102001) for financial supports.
1 1-Butyl-1-cyclohexylpyrrolidinium;
2 1-Cyclohexyl-1-methylpyrrolidinium;
3 1-Cyclohexyl-1-ethylpyrrolidinium; References
4 1-Butyl-1-cyclooctylpyrrolidinium;
5 1-Butyl-1-cyclooctyl-3-methylpyrrolidinium; 1 J. Čejka, A. Corma and S. Zones, Zeolites and Catalysis:
6 (2 0 R,6 0 S)-2 0 ,6 0 -Dimethylspiro[isoindoline-2,1 0 -piperidin]- Synthesis Reactions and Applications, Wiley, Weinheim, 2010.
1 0 -ium hydroxide; 2 M. E. Davis, Nature, 2002, 417, 813–821.

Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2015
 View Article Online

Chem Soc Rev Review Article

3 R. M. Barrer, J. Chem. Soc., 1948, 127–132. 32 K. Qian, J. Li, J. Jiang, Z. Liang, J. Yu and R. Xu, Microporous
4 C. S. Cundy and P. A. Cox, Microporous Mesoporous Mater., Mesoporous Mater., 2012, 164, 88–92.
2005, 82, 1–78. 33 M. Moliner, J. González, M. T. Portilla, T. Willhammar,
5 Z. Wang, J. Yu and R. Xu, Chem. Soc. Rev., 2012, 41, F. Rey, F. J. Llopis, X. Zou and A. Corma, J. Am. Chem. Soc.,
1729–1741. 2011, 133, 9497–9505.
6 J. Yu and R. Xu, Acc. Chem. Res., 2010, 43, 1195–1204. 34 T. Willhammar, J. Sun, W. Wan, P. Olevnikov, D. Zhang,
7 M. Moliner, F. Rey and A. Corma, Angew. Chem., Int. Ed., X. Zou, M. Moliner, J. Gonzalez, C. Martı́nez, F. Rey and
2013, 52, 13880–13889. A. Corma, Nat. Chem., 2012, 4, 188–194.
Published on 05 March 2015. Downloaded by University of Western Ontario on 09/03/2015 01:28:10.

8 J. Li, J. Yu and R. Xu, Proc. R. Soc. A, 2012, 468, 1955–1967. 35 M. Moliner, T. Willhammar, W. Wan, J. González, F. Rey,
9 W. J. Roth, P. Nachtigall, R. E. Morris and J. Čejka, Chem. J. L. Jorda, X. Zou and A. Corma, J. Am. Chem. Soc., 2012,
Rev., 2014, 114, 4807–4837. 134, 6473–6478.
10 U. Dı́az and A. Corma, Dalton Trans., 2014, 43, 10292–10316. 36 D. L. Dorset, K. G. Strohmaier, C. E. Kliewer, A. Corma,
11 M. B. Park, S. J. Cho and S. B. Hong, J. Am. Chem. Soc., M. J. Dı́az-Cabañas, F. Rey and C. J. Gilmore, Chem. Mater.,
2011, 133, 1917–1934. 2008, 20, 5325–5331.
12 Y. Li and J. Yu, Chem. Rev., 2014, 114, 7268–7316. 37 D. L. Dorset, G. J. Kennedy, K. G. Strohmaier, M. J. Dı́az-
13 C. Baerlocher and L. B. McCusker, Database of Zeolite Cabañas, F. Rey and A. Corma, J. Am. Chem. Soc., 2006, 128,
Structures, http://www.iza-structure.org/databases/. 8862–8867.
14 J. Jiang, J. Yu and A. Corma, Angew. Chem., Int. Ed., 2010, 38 A. Corma, M. J. Dı́az-Cabañas, J. L. Jordá, F. Rey, G. Sastre and
49, 3120–3145. K. G. Strohmaier, J. Am. Chem. Soc., 2008, 130, 16482–16483.
15 S. Elomari, US Pat., 6 616 911, 2003. 39 T. Boix, M. Puche, M. A. Camblor and A. Corma, US Pat., 6
16 S. Elomari, US Pat., 6 544 495, 2003. 471 941, 2002.
17 C. Baerlocher, T. Weber, L. B. McCusker, L. Palatinus and 40 M. Hernández-Rodrı́guez, J. L. Jordá, F. Rey and A. Corma,
S. I. Zones, Science, 2011, 333, 1134–1137. J. Am. Chem. Soc., 2012, 134, 13232–13235.
18 A. Burton, S. Elomari, R. C. Medrud, I. Y. Chan, C. Y. Chen, 41 R. Simancas, J. L. Jordá, F. Rey, A. Corma, A. Cantı́n, I. Peral
L. M. Bull and E. S. Vittoratos, J. Am. Chem. Soc., 2003, 125, and C. Popescu, J. Am. Chem. Soc., 2014, 136, 3342–3345.
1633–1642. 42 R. Martı́nez-Franco, M. Moliner, Y. Yun, J. Sun, W. Wan,
19 J. Jiang, J. L. Jordá, J. Yu, L. A. Baumes, E. Mugnaioli, X. Zou and A. Corma, Proc. Natl. Acad. Sci. U. S. A., 2013,
M. J. Dı́az-Cabañas, U. Kolb and A. Corma, Science, 2011, 110, 3749–3754.
333, 1131–1134. 43 S. I. Zones, Zeolites, 1989, 9, 458–467.
20 J. Jiang, Y. Xu, P. Cheng, Q. Sun, J. Yu, A. Corma and R. Xu, 44 P. A. Barrett, T. Boix, M. Puche, D. H. Olson, E. Jordan, H. Köller
Chem. Mater., 2011, 23, 4709–4715. and M. A. Camblor, Chem. Commun., 2003, 2114–2115.
21 D. Xie, L. B. McCusker, C. Baerlocher, S. I. Zones, W. Wan 45 Y. Lorgouilloux, M. Dodin, J. L. Paillaud, P. Caullet,
and X. Zou, J. Am. Chem. Soc., 2013, 135, 10519–10524. L. Michelin, L. Josien, O. Ersen and N. Bats, J. Solid State
22 S. Smeets, D. Xie, C. Baerlocher, L. B. McCusker, W. Wan, Chem., 2009, 182, 622–629.
X. Zou and S. I. Zones, Angew. Chem., Int. Ed., 2014, 53, 46 M. Dodin, J.-L. Paillaud, Y. Lorgouilloux, P. Caullet, E. Elkaı̈m
10398–10402. and N. Bats, J. Am. Chem. Soc., 2010, 132, 10221–10223.
23 S. Elomari, A. W. Burton, K. Ong, A. R. Pradhan and 47 L. Tang, L. Shi, C. Bonneau, J. Sun, H. Yue, A. Ojuva, B. L.
I. Y. Chan, Chem. Mater., 2007, 19, 5485–5492. Lee, M. Kritikos, R. G. Bell, Z. Bacsik, J. Mink and X. Zou,
24 S. I. Zones, A. W. Burton and K. Ong, International Pat., WO Nat. Mater., 2008, 7, 381–385.
2007/079038, 2007. 48 A. Rojas and M. A. Camblor, Angew. Chem., Int. Ed., 2012,
25 E. Benazz, J. L. Guth and L. Rouleau, Patent Cooperation 51, 3854–3856.
Treaty, WO 98/17581, 1998. 49 A. Corma, F. Rey, J. Rius, M. J. Sabater and S. Valencia,
26 S. B. Hong, E. G. Lear, P. A. Wright, W. Zhou, P. A. Cox, Nature, 2004, 431, 287–290.
C. H. Shin, J. H. Park and I. S. Nam, J. Am. Chem. Soc., 2004, 50 F. Chen, Y. Xu and H. Du, Angew. Chem., Int. Ed., 2014, 53,
126, 5817–5826. 9592–9596.
27 A. Jackowski, S. I. Zones, S. J. Hwang and A. W. Burton, 51 K. J. Balkus and A. G. Gabrielov Jr., US Pat., 5 489 424, 1996.
J. Am. Chem. Soc., 2009, 131, 1092–1100. 52 Y. Han, Y. Li, J. Yu and R. Xu, Angew. Chem., Int. Ed., 2011,
28 A. W. Burton, US Pat., 7 820 141, 2010. 50, 3003–3005.
29 Y. Lorgouilloux, M. Dodin, E. Mugnaioli, C. Marichal, 53 Y. Xu, Y. Li, Y. Han, X. Song and J. Yu, Angew. Chem.,
P. Caullet, N. Bats, U. Kolb and J. Paillaud, RSC Adv., Int. Ed., 2013, 52, 5501–5503.
2014, 4, 19440–19449. 54 R. Martı́nez-Franco, M. Moliner, C. Franch, A. Kustov and
30 M. Afeworki, D. L. Dorset, G. J. Kennedy and K. G. A. Corma, Appl. Catal., B, 2012, 127, 273–280.
Strohmaire, Chem. Mater., 2006, 18, 1697–1704. 55 R. Martı́nez-Franco, M. Moliner, J. R. Thogersen and
31 J. Sun, C. Bonneau, Á. Cantı́n, A. Corma, M. J. Dı́az- A. Corma, ChemCatChem, 2013, 5, 3316–3323.
Cabañas, M. Moliner, D. Zhang, M. Li and X. Zou, Nature, 56 R. Martı́nez-Franco, M. Moliner, P. Concepcion, J. R.
2009, 458, 1154–1157. Thogersen and A. Corma, J. Catal., 2014, 314, 73–82.

This journal is © The Royal Society of Chemistry 2015 Chem. Soc. Rev.
 View Article Online

Review Article Chem Soc Rev

57 R. Martı́nez-Franco, M. Moliner and A. Corma, J. Catal., 84 S. Correll, O. Oeckler, N. Stock and W. Schnick, Angew.
2014, 319, 36–43. Chem., Int. Ed., 2003, 42, 3549–3552.
58 L. Ren, L. Zhu, C. Yang, Y. Chen, Q. Sun, H. Zhang, C. Li, 85 S. J. Sedlmaier, M. Döblinger, O. Oeckler, J. Weber,
F. Nawaz, X. Meng and F. Xiao, Chem. Commun., 2011, 47, J. Schmedt auf der Günne and W. Schnick, J. Am. Chem.
9789–9791. Soc., 2011, 133, 12069–12078.
59 Y. Li, J. Yu and R. Xu, Angew. Chem., Int. Ed., 2013, 52, 1673–1677. 86 B. Marler and H. Gies, Eur. J. Mineral., 2012, 24, 405–428.
60 X. Song, Y. Li, L. Gan, Z. Wang, J. Yu and R. Xu, Angew. 87 A. J. Blake, K. R. Franklin and B. M. Lowe, J. Chem. Soc.,
Chem., Int. Ed., 2009, 48, 314–317. Dalton Trans., 1988, 2513–2517.
Published on 05 March 2015. Downloaded by University of Western Ontario on 09/03/2015 01:28:10.

61 Z. Liu, X. Song, J. Li, Y. Li, J. Yu and R. Xu, Inorg. Chem., 88 M. E. Leonowicz, J. A. Lawton, S. L. Lawton and M. K.
2012, 51, 1969–1974. Rubin, Science, 1994, 264, 1910–1913.
62 L. Shao, Y. Li, J. Yu and R. Xu, Inorg. Chem., 2012, 51, 225–229. 89 T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai and F. Mizukami,
63 R. W. Broach, N. Greenlay, P. Jakubczak, L. M. Knight, Angew. Chem., Int. Ed., 2004, 43, 4892–4896.
S. R. Miller, J. P. S. Mowat, J. Stanczyk and G. J. Lewis, 90 B. Marler, Y. Wang, J. Song and H. Gies, Dalton Trans.,
Microporous Mesoporous Mater., 2014, 189, 49–63. 2014, 43, 10396–10416.
64 A. Corma, M. J. Dı́az-Cabañas, J. Jiang, M. Afeworki, D. L. 91 S. Zanardi, A. Alberti, G. Cruciani, A. Corma, V. Fornés and
Dorset, S. L. Soled and K. G. Strohmaier, Proc. Natl. Acad. M. Brunelli, Angew. Chem., Int. Ed., 2004, 43, 4933–4937.
Sci. U. S. A., 2010, 107, 13997–14002. 92 Y. X. Wang, H. Gies, B. Marler and U. Müller, Chem. Mater.,
65 J. Jiang, J. L. Jordá, M. J. Dı́az-Cabañas, J. Yu and A. Corma, 2005, 17, 43–49.
Angew. Chem., Int. Ed., 2010, 49, 4986–4988. 93 B. Marler, N. Ströter and H. Gies, Microporous Mesoporous
66 W. Hua, H. Chen, Z. Yu, X. Zou, J. Lin and J. Sun, Angew. Mater., 2005, 83, 201–211.
Chem., Int. Ed., 2014, 53, 5868–5871. 94 P. Wu, J. Ruan, L. Wang, L. Wu, Y. Wang, Y. Liu, W. Fan,
67 J. Jiang, Y. Yun, X. Zou, J. L. Jordá and A. Corma, Chem. M. He, O. Terasaki and T. Tatsumi, J. Am. Chem. Soc., 2008,
Sci., 2015, 6, 480–485. 130, 8178–8187.
68 F. Gao, M. Jaber, K. Bozhilov, A. Vicente, C. Fernandez and 95 H. Gies, U. Müller, B. Yilmaz, T. Tatsumi, B. Xie, F. Xiao,
V. Valtchev, J. Am. Chem. Soc., 2009, 131, 16580–16586. X. Bao, W. Zhang and D. D. Vos, Chem. Mater., 2011, 23,
69 L. B. McCusker, R. W. Grosse-Kunstleve, C. Baerlocher, 2545–2554.
M. Yoshikawa and M. E. Davis, Microporous Mater., 1996, 6, 96 H. Gies, U. Müller, B. Yilmaz, M. Feyen, T. Tatsumi, H. Imai,
295–309. W. Zhang, B. Xie, F. Xiao, X. Bao, W. Zhang, T. D.
70 Y. Lee, S. J. Kim, G. Wu and J. B. Parise, Chem. Mater., 1999, Baerdemaeker and D. D. Vos, Chem. Mater., 2012, 24, 1536–1545.
11, 879–881. 97 T. D. Baerdemaeker, H. Gies, B. Yilmaz, U. Müller,
71 K. G. Strohmaier and D. E. W. Vaughan, J. Am. Chem. Soc., M. Feyen, F. Xiao, W. Zhang, T. Yokoi, X. Bao and D. D.
2003, 125, 16035–16039. Vos, J. Mater. Chem. A, 2014, 2, 9709–9717.
72 A. Burton, S. Elomari, R. C. Medrud, I. Y. Chan, C. Y. Chen, 98 W. J. Roth, O. V. Shvets, M. Shamzhy, P. Chlubná, M. Kubù,
L. M. Bull and E. S. Vittoratos, J. Am. Chem. Soc., 2003, 125, P. Nachtigall and J. Èejka, J. Am. Chem. Soc., 2011, 133,
1633–1642. 6130–6133.
73 A. Burton, S. Elomari, C.-Y. Chen, R. C. Medrud, I. Y. Chan, 99 E. Verheyen, L. Joos, K. Van Havenbergh, E. Breynaert,
L. M. Bull, C. Kibby, T. V. Harris, S. I. Zone and E. S. N. Kasian, E. Gobechiya, K. Houthoofd, C. Martineau,
Vittoratos, Chem. – Eur. J., 2003, 9, 5737–5748. M. Hinterstein, F. Taulelle, V. V. Speybroeck, M. Waroquier,
74 A. Burton and S. Elomari, Chem. Commun., 2004, 2618–2619. S. Bals, G. Van Tendeloo, C. E. A. Kirschhock and J. A.
75 J. A. Armstrong and M. T. Weller, J. Am. Chem. Soc., 2010, Martens, Nat. Mater., 2012, 11, 1059–1064.
132, 15679–15686. 100 W. J. Roth, P. Nachtigall, R. E. Morris, P. S. Wheatley,
76 S. H. Park, H. Liu, M. Kleinsorge, C. P. Grey, B. H. Toby and V. R. Seymour, S. E. Ashbrook, P. Chlubná, L. Grajciar,
J. B. Parise, Chem. Mater., 2004, 16, 2605–2614. M. Položij, A. Zukal, O. Shvets and J. Èejka, Nat. Chem.,
77 S. H. Park, H. Gies, B. H. Toby and J. B. Parise, Chem. 2013, 5, 628–633.
Mater., 2002, 14, 3187–3196. 101 Z. Zhao, W. Zhang, P. Ren, W. Han, U. Müller, B. Yilmaz,
78 S. H. Park, P. Daniels and H. Gies, Microporous Mesoporous M. Feyen, H. Gis, F. Xiao, D. D. Vos, T. Tatsumi and X. Bao,
Mater., 2000, 37, 129–143. Chem. Mater., 2013, 25, 840–847.
79 S. H. Park, J. B. Parise, H. Gies, H. Liu, C. P. Gery and 102 J. L. Jordá, F. Rey, G. Sastre, S. Valencia, M. Palomino,
B. H. Toby, J. Am. Chem. Soc., 2000, 122, 11023–11024. A. Corma, A. Segura, D. Errandonea, R. Lacomba, F. J.
80 Y. Li and X. Zou, Angew. Chem., Int. Ed., 2005, 44, 2012–2015. Manjón, O. Gomis, A. K. Kleppe, A. P. Jephcoat,
81 J. Su, Y. Wang, Z. Wang and J. Lin, J. Am. Chem. Soc., 2009, M. Amboage and J. A. Rodrı́guez-Velamazán, Angew. Chem.,
131, 6080–6081. Int. Ed., 2013, 52, 10458–10462.
82 W. Schnick and J. Lücke, Angew. Chem., Int. Ed., 1992, 31, 103 M. D. Foster and M. M. J. Treacy, A Database of Hypothetical
213–215. Zeolite Structures, http://www.hypotheticalzeolites.net.
83 N. Stock, E. Irran and W. Schnick, Chem. – Eur. J., 1998, 4, 104 Y. Li, J. Yu and R. Xu, Hypothetical Zeolite Database,
1822–1828. http://mezeopor.jlu.edu.cn/hypo.

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