Perspective

pubs.acs.org/cm

Zeolites from a Materials Chemistry Perspective

Mark E. Davis
Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States

ABSTRACT: Zeolites and zeolite-like materials are continually

finding new applications. Because of the uniformity of these solids,
the expression of macroscale materials properties that are
controlled by the materials chemistry at the atomic/molecular
scale are achievable. In this Perspective, I discuss the following areas
of current interest in zeolites and zeolite-like materials that rely on
manipulation of the materials chemistry for their preparation and
provide new opportunities for application: (i) exploitation of
organic structure-directing agents (SDAs) for new materials, (ii)
the synthesis of zeolites without SDAs, (iii) the synthesis of very
hydrophobic materials, (iv) conversions of two-dimensional (2D)
to 3D materials and vice versa, (v) hierarchically organized
materials, (vi) chiral materials, and (vii) direction of tetrahedral
atoms to specific framework positions.
KEYWORDS: zeolites, synthesis, applications, future

■ INTRODUCTION
It is my pleasure to provide this Perspective on the materials
QuikClot contains a dehydrated zeolite that was approved for
use by the FDA in 2002.4,5 It is currently being used by the
chemistry of zeolites for the 25 Year Celebratory Special Issue military and emergency personnel and can even be purchased
of Chemistry of Materials. As a previous editor of this journal, I for consumer use. In addition to preparing zeolites with specific
have closely watched its evolution. I am excited by the many pore sizes for shape-selective adsorption/catalysis, zeolites can
developments in materials chemistry over the past few decades be modified in order to tune their surface properties. An
and feel that Chemistry of Materials has been a showcase for the interesting application of the tuned adsorption properties of a
field. In 1992, Raul Lobo and I published an extensive review zeolite is in the wine industry. The contamination of wine with
on “Zeolite and Molecular Sieve Synthesis” in Chemistry of 2,4,6-trichloroanisole (TCA), known as “cork taint,” is an
Materials.1 That review has now been cited over 750 times increasing problem for wine producers. A zeolite with particular
(Web of Knowledge, June 2013) and continues to be cited adsorption properties is now being used to remove TCA from
today. In that review, Raul and I summarized zeolite and wine without altering its taste.6
molecular sieve synthesis in order to identify significant trends An area that has emerged since our review is that of
and suggest future areas of research. Also, we discussed the hydrophobic materials. The chemistry of the zeolite materials
plausibility of new types of materials that may be achievable can now be controlled to provide very hydrophobic solids that
through designed, synthetic efforts. Here, I provide a can perform a number of new applications. I will discuss this
perspective on zeolites and zeolite-like materials and emphasize topic further and illustrate a new and unanticipated application
how the materials chemistry drives new properties and new in the context of new catalysis below. However, the use of
applications. A few of these issues that have emerged over the hydrophobic materials as adsorbents to remove organic
past decades are ones that Raul and I discussed and got right, compounds such as methyltertbutylether (MTBE) and
while others have been totally unanticipated. chlorinated hydrocarbons like 1,2-dichloroethane and chlor-
Zeolites and molecular sieves continue to find more and new obenzenes has already been commercialized.7,8
uses in commercial applications.2 The traditional areas of In our 1992 review, Raul and I presented numerous issues
zeolite and molecular sieve use, such as ion exchangers, with zeolites in the context of their materials synthesis and/or
adsorbents, and catalysts (for example, with catalysis, see ref 3), properties. For example, at that time, extra-large pore materials
all continue to grow. In addition to these more traditional (crystalline molecular sieves with pores composed of greater
applications (that have been used by traditional industries like
the petrochemicals industries), there are now many other uses
Special Issue: Celebrating Twenty-Five Years of Chemistry of
outside those areas and industries. For example, low Si/Al
Materials
zeolites are very hydrophilic and well-known to adsorb water.
Most of us have used them at some point to dehydrate organic Received: June 12, 2013
solvents. The ability of zeolites to adsorb water (along with Revised: August 29, 2013
other features) has led to their use as a blood-clotting agent.

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Chemistry of Materials Perspective

than 12 oxygen atoms that can give pore sizes above 1 nm) Work continues on understanding how the properties of the
were just emerging. These materials were prepared as SDAs lead to the production of crystalline structures.14−17
aluminophosphate compositions. We suggested at that time Since synthetic organic chemistry is quite advanced, the ability
that large organic structure-directing agents (SDAs) could likely to understand what properties of the organic SDAs provide for
lead to silica-based, extra-large pore materials with significantly good structure direction remains crucial to future successes.
different properties from the aluminophosphates. This has The diversity of organic molecules that are being utilized as
indeed occurred.9,10 However, we did not anticipate the SDAs is ever increasing (a recent example involves organic
discovery of the ordered mesoporous materials in that review. molecules that are proton sponges18). Of importance is the fact
Thus, the development of many types of porous materials with that the inorganic chemistry cannot be ignored when exploiting
pores larger than 1 nm in diameter has occurred and will not be the concept of structure direction.17,19 It is the correct
discussed further here. combination of SDAs and inorganic chemistry that are married
Interestingly, not only has there been a movement to larger together in the assembly processes to create the final structures.
pore materials, but also much work has occurred with small In 1991, Raul and I asked the question, “can zeolite synthesis be
pore materials (pores composed of 8 oxygen atoms). This is designed?” At that time, the answer was no. Today, the answer
because of the discovery of materials like SAPO-34 that now remains no, but the field is moving closer to being able to
commercially convert methanol to primarily ethylene and produce structures with given properties by design, e.g., pore
propylene in China, and Cu-SSZ-13 that is now used sizes and presence or absence of cages.
commercially as a deNOx catalyst (these topics will be covered A particularly interesting methodology that illustrates the
elsewhere in this issue of Chemistry of Materials). Here, I am importance of having both the “right” organic molecule and the
going to discuss the following topics as they are emerging areas “right” inorganic chemistry is now called the charge density
of current interest that all rely on manipulation of the materials mismatch (CDM) approach.20 The concept of CDM involves
chemistry for their preparation and provide new opportunities creating a synthesis mixture that contains an organic agent like
for application: (i) exploitation of SDAs for new materials, (ii) a tetraethylammonium cation. The mixtures are heated, but
the synthesis of zeolites without SDAs, (iii) the synthesis of they do not produce a crystalline material due to a number of
very hydrophobic materials, (iv) conversions of 2D to 3D reasons, including a large mismatch in charge that would be
materials and vice versa, (v) hierarchically organized materials, required if a structure were to form via structure direction of
(vi) chiral materials, and (vii) direction of tetrahedral atoms to the organic cation. When additional organic molecules, e.g.,
specific framework positions. The latter two topics have not yet tetramethylammonium cations, are added, these “precursor”
been realized but are of high current and future interest.

■
mixtures then crystallize into a solid. This approach has
provided a number of new structures that have higher
SYNTHESIS OF ZEOLITES AND MOLECULAR aluminum contents than normally achieved with the use of
SIEVES traditional syntheses employing SDAs.20,21
Structure Direction via the Use of Organic Species. When an organic SDA is used to crystallize a molecular sieve
The synthesis of zeolites and molecular sieves can involve the of interest, the cost of the organic is often thought to be
use of organic molecules that influence the crystal assembly prohibitive of commercialization. Zones has recently discussed
processes. The term “templating” has been used in this context this issue.2 Two synthetic methods have been developed to
in the past. Raul and I suggested that true templating may have address the use of costly organic SDAs. Lee et al. showed that
occurred in only one case (ZSM-18) at the time of our review. recyclable SDAs can be prepared.22 For example, the synthesis
We emphasized that the organic molecules that were described of ZSM-5 has been illustrated with this methodology using a
in the literature as templates should be thought of as structure- SDA that contains a cyclic ketal group that is removed from the
directing agents (SDAs) rather than as true templates. To date, SDA while in the pores of the formed ZSM-5 (Figure 1). The
I believe that there is no example of true templating, as the one remaining organic is then small enough to be removed via ion
example we mentioned previously1 has now been shown to not exchange. The collected organic fragments are then reas-
be templating but rather what we would classify as structure sembled and used again. This method has not yet been
direction. commercialized. A second approach exploits the use of two
The concept of structure direction via organic molecules has organic molecules in the synthesis. The expensive SDA is used
provided a wealth of new structures with new properties.
Previously, we suggested that the synthesis of extra-large pore
materials via appropriately sized organic SDAs could occur.
This has indeed happened, and there are several examples of
extra-large pore materials, e.g., UTD-1, CIT-5, and SSZ-53,10
that have been synthesized via the use of large organic SDAs. In
addition to creating extra-large pore materials, the use of SDAs
also enabled the synthesis of molecular sieves that have
intersecting 12 and 10 member-ring pores. This pore
architecture is particularly desirable for certain catalytic
reactions, and we speculated that these structures could be
synthesized because the natural zeolite Boggsite has a pore
system of this type.11 Through the use of SDAs, materials with
12−10 pore systems have been prepared. SSZ-33 and SSZ-26
were the first synthetic structures of this type,12 and there are
now many others. In fact, even the synthetic analog of Boggsite
has now been prepared using an organic SDA.13 Figure 1. Schematic representation a recyclable SDA. From ref 22.

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Chemistry of Materials Perspective

to nucleate the synthesis, and a second organic molecule that is calcination that involves environmental concerns over the
much less costly is utilized in the crystal growth process to fill exhaust gases that can contain toxic oxides of carbon and
the internal void space (Figure 2). Zones provides a nice nitrogen).
The zeolite ECR-1, normally prepared via the use of organic
SDAs, was synthesized without an organic SDA in 2006.23
Interestingly, the Si/Al of the organic-free synthesis was the
same as that from the preparation using organic SDAs (Si/Al =
14). The organic-free synthesis was obtained by elucidating a
specific inorganic mixture. Thus, this methodology would be
difficult to generalize to other structures.
A more generalized approach to the synthesis of zeolites that
were originally prepared with organic SDAs, but now prepared
in their absence, exploits seeding the reaction mixture. Xie et al.
first prepared zeolite beta without the use of an organic SDA in
2008.24 While the natural mineral tschernichite exists and has
the zeolite beta structure,25 the preparation of organic-free
zeolite beta is a significant breakthrough in zeolite synthesis.
The Si/Al of tschernichite is ca. 3. Thus, the zeolite beta
Figure 2. Schematic representation of the use of a SDA and another structure is able to exist with this low Si/Al. The organic-free
organic molecule that can fill pore space during the synthesis of a
zeolite.2
syntheses of zeolite beta give Si/Al as low as ca. 5,26 whereas
the SDA mediated syntheses all give values larger than 10. The
seed-assisted synthesis of organic-free zeolites has now been
example of this method showing how a much less expensive
organic cation can be used in combination with a series of more reported for a number of zeolites that had previously only been
expensive organic cations to produce a series of structures prepared via the use of an organic SDA, e.g., ZSM-11,27 ZSM-
(SSZ-13, SSZ-35, SSZ-33, SSZ-42).2 This methodology has 12,28 and RUB-13.29 Thus, it appears that the use of seed-
been used to commercialize the synthesis of molecular sieves.2 assisted synthesis can be applied to prepare a variety of zeolite
Thus, there continues to be strong efforts in creating new structures. Lower Si/Al products may not be as useful as their
structures and/or existing structures with new properties via the higher Si/Al analogs. This is likely the case for their use as
use of structure direction. Bias against this method of synthesis catalysts. However, aluminum can be removed from the lower
because of perceived cost barriers is declining for the reasons Si/Al materials (this requires further chemical processing) to
outlined by Zones.2 provide useful catalytic materials.30
Synthesis in the Absence of Organic SDAs. The first The use of organic SDA-free syntheses of zeolites provides a
synthetic zeolites were aluminum-rich and prepared using alkali number of advantages for scale up and commercialization.
metal cations.1 Higher Si/Al zeolites are normally obtained However, there are also downsides to this type of synthesis.
when using organic SDAs, as these cations are larger than alkali High yields are typically not achieved with these types of
cations (less framework charge needed to balance their positive preparations even when high amounts of seeds (ca. 10 wt %)
charge) and they are more hydrophobic (the larger the Si/Al, are used, and control of the product Si/Al and crystal sizes are
the more hydrophobic is the pore space). Recently, there are difficult. Thus, one needs to consider the trade-offs of preparing
renewed efforts to synthesize zeolites and molecular sieves zeolites with methods using organic SDAs like those described
without the use of organic SDAs. The advantages of doing so by Zones2 to the lower yields of the organic SDA-free
are the elimination of the organic SDA cost and the need to syntheses. Higher yields may be achievable using synthetic
remove the organic species prior to use (normally through air methods that do not involve bulk solvent,31 but it is not clear

Figure 3. Stereoselective reactions accomplished in water with hydrophobic zeolites.

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Chemistry of Materials Perspective

Figure 4. Illustration of methods to form porous materials from layered precursors. From ref 47.

how this type of preparation could be accomplished at large H2O/SiO2 that exceed 10 and often can reach into the 100s
scale. Also, zeolites are not used in their as-synthesized form in (for some clear solution syntheses). What is surprising about
applications, so subsequent steps like ion change, etc. will these low water content syntheses is that they tend to produce
require processes involving solvents. Thus, it is not clear how zeolites and molecular sieves with high porosity. The
the lack of a bulk solvent in the synthesis step would influence fundamental reasons behind this trend remain unknown.
the overall process of preparing a zeolite material for However, Zones and co-workers have shown that the lower
application. water amounts in the synthesis media do lead to frameworks of
Synthesis Using F− as the Mineralizing Agent Rather lower framework density and that these frameworks contain a
than OH−. In our 1991 review of zeolite synthesis, we greater number of rings with four tetrahedral atoms.39
discussed the emerging use of F− as a mineralizing agent (HF, Additionally, this type of synthesis has led to the crystallization
NaF, NH4F) for zeolite and molecular sieve synthesis.1 While of new and interesting structures. For example, a pure silica
initially discovered by Flanigen and Patton in 1978, this structure with a helical pore system has recently been
synthetic method was developed further by Guth and Kessler in reported.40 I will discuss this structure further in the section
the late 1980s and early 1990s.1 Two issues of importance have on chirality.
emerged since that time.
First, the high silica structures that are prepared using organic
SDAs in F− media have low defect density (internal silanol
■ ZEOLITE AND MOLECULAR SIEVE
ARCHITECTURES AND ARRANGEMENTS
groups) because the F− balances the positive charge of the SDA 2D to 3D Structures and Vice Versa. Numerous zeolite
rather than creating a defect in the structure to perform the structures can be visualized as layers that are connected to form
balancing.32 Because of the low internal defect density, the the three-dimensional framework. Early attempts to create
structures can be very hydrophobic.33,34 The ability to create framework silicates by topotactic condensation of layered
hydrophobic environments within the pore system of the silicates such as magadiite were described by Lagaly et al.41 The
materials has opened new applications in adsorption and structures of the materials formed could not be solved, so it
catalysis. For example, glucose can be isomerized to fructose in remains unknown whether true frameworks were prepared at
bulk aqueous solvent using a zeolite beta that is hydrophobic that time. Since then, there have been several successes in
and contains Lewis acid sites created by either framework Ti4+ synthesizing framework materials by topotactic condensation of
or Sn4+ substitutions for Si4+.35 The catalysis proceeds by a layered precursor materials. Marler and Gies provide an
mechanism that is analogous to that which occurs with excellent review of this area.42 The first successful zeolite
metalloenzymes.36 Some of the key features of both the zeolite material prepared from a 2D material was MCM-22.43 The
and the enzyme catalysis are a Lewis acid mediated intra- precursor to MCM-22 (MCM-22(P)) contains one unit cell
molecular hydride shift that is accomplished in a hydrophobic thick layers separated by organic molecules that were used as
environment of the catalyst.35,36 Thus, the ability to create SDAs in the synthesis. Upon calcining MCM-22(P), the layers
hydrophobic zeolites by the use of F− mediated syntheses is condense to form the MCM-22 framework (3D-MWW)
opening the area of Lewis acid catalysis in water.37 The types of (Figure 4). This discovery opened numerous synthetic
stereoselective reactions that have been reported over these pathways to produce porous materials. The pillaring of clays
hydrophobic catalysts are shown in Figure 3. and other layered materials has been explored for many
Second, Camblor and co-workers have shown that, with F−- decades. We pillared layered silicates with silanes in attempts to
based syntheses, the amount of water that is necessary for create organosilicate precursors that upon calcination might
crystallization can be very small.38 For example, a variety of form framework structures.44 As with the materials prepared by
different materials can be synthesized in F− media with water Lagaly et al., we were not able to solve the structures of these
contents below a H2O/SiO2 of 10 (values can even be as low as new microporous materials. Thus, we were not able to prove
1).38 Typical OH-mediated zeolite syntheses have values of that framework silicates could be formed via this synthetic
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Chemistry of Materials Perspective

methodology. However, the use of precursor materials like not controllable, and often, the composition of the remaining
MCM-22(P) enabled the creation of delaminated structures regions that have microporosity may not be at the framework
(ITQ-2) that in principle could be only one layer45 or pillared composition that is required. To overcome these limitations,
materials that gave well-defined 3D solids (MCM-36).46 These there have been a variety of methods developed to create
synthetic methods (illustrated in Figure 4 with MCM-22(P)) hierarchically organized microporous materials with greater
have been used to form a variety of materials starting from control on the arrangement of the microporous and
layered precursors other than MCM-22(P); e.g., the FER mesoporous areas of the material.
precursor (PREFER) can be delaminated to give ITQ-6 or Numerous techniques have been used to create hierarchically
pillared to prepare ITQ-36.47 Reviews on these methods of organized microporous materials, and several recent reviews on
preparation and the structures and properties of the 3D this topic are available.57−59 Some of these methods use
materials formed are available.47−49 This area of materials sophisticated structure directing agents. For example, Ryoo and
synthesis is quite active, and precursor 2D materials like MCM- co-workers first introduced the use of an organosilane that
22(P) continue to provide for new materials.49 Synthetic issues contains three structural features: (i) an alkoxysilane terminus
such as the control of the pillaring and exfoliation processes that gets incorporated into the final inorganic structure, (ii) an
remain important topics of research.50 adjacent quaternary ammonium group that is used to structure
Recently, there have been studies involved in deconstructing direct a unit cell of a zeolite (e.g., MFI), and (iii) an alkyl tail
3D frameworks into 2D solids. Previous attempts to perform that then is used to create the mesopore configuration.57−59
the 3D to 2D transformations using silicate and zeolites have These types of SDAs can produce hierarchically organized
not led to well-defined solids. However, the use of framework microporous materials of controllable thickness and with fairly
germanosilicates has enabled the 3D to 2D transformation.51 uniform mesopores that can be tuned by the size of the alkyl
Chlubna et al. used this concept to convert the framework tail. Additionally, the use of a SDA allowed for the growth of
structure UTL to a layered solid (Ge removed from four- hierarchically organized MFI zeolites with plate-like morphol-
membered rings).52 The layered material was then pillared and ogy and 90 degree rotational intergrowths.60,61 The meso-
calcined to yield high surface area solids with both micropores porosity created via the two synthetic methods used to create
and mesopores. Verheyen et al. prepared the framework these MFI-based materials is significantly different. Addition-
material IM-12 that has four-membered rings that connect ally, Tsapatsis and co-workers have recently demonstrated that
layers in the structure.53 By synthesizing the material such that tetrabutylammonium cations can be used as the SDAs for their
the four-membered rings contain Ge and the layers Si, the Ge preparation.62 While these hierarchically organized materials are
could be acid leached from the framework material to produce scientifically interesting and quite elegant, the question remains
a layered solid (Si−O−Ge and Ge−O−Ge linkages are more as to whether there are any technical advantages to the use of
readily hydrolyzed than Si−O−Si). Calcination annealed the these materials over those that have randomly oriented
layered structure to create a new 3D framework.53 Likewise, mesopores. Because these materials will be much more costly
Roth et al. disassembled the framework UTL and reassembled to prepare (although the recent work by Tsapatsis et al.62 could
the formed layers into two different framework materials.54 change this), their application will most likely have to be for a
This is an exciting new area of synthesis that should open use that takes advantage of the uniformity of the overall
pathways to structures that may not be obtainable via standard structure. In many ways, this argument is similar to that for the
hydrothermal synthesis. application of the ordered mesoporous materials. That is, one
Hierarchically Organized Microporous Materials. The must find an application that utilizes the uniformity in the pore
exploitation of the microporosity in zeolites and zeolite-like system in order to justify the added cost of production over
materials has led to a number of commercial applications like solids that have nonuniform porosity.

■
shape selective adsorption (e.g., adsorb only linear molecules in
the presence of branched molecules) and catalysis (e.g.,
AREAS FOR FUTURE INVESTIGATION
production of para-xylene). However, the creation of hierarchi-
cally organized microporous materials, that is, materials with a Chiral Structures. In our 1992 review, Raul and I
secondary porosity (most typically mesoporosity) that is concluded the presentation with a discussion on the possibility
connected to the microporosity, can produce materials that of creating chiral zeolites.1 To date, no one has synthesized a
outperform purely microporous materials in certain applica- sample of a powder that is an enantiomerically pure, chiral
tions. For example, the observed catalytic rates from zeolites zeolite. This goal remains elusive, and I describe some of the
with mesopores can be larger than those with only micropores progress that has occurred since 1992 in this area.
due to the increased transport rates in the mesopores that Chiral, crystalline frameworks and layered materials do exist.
connect to the micropores where the shape selective reactions With zeolites or zeolite-like materials, we first reported a slight
can occur. In the past, hierarchically organized microporous enantioselectivity from a zeolite beta that was synthesized using
materials were prepared via dealumination (by steaming and/or a chiral structure directing agent.1 Zeolite beta is an intergrowth
acid treatments; see, for example, the work by Janssen et al. on of two polymorphs (A and B), and one (A) has enantiomorphs.
three-dimensional transmission electron microscopy of deal- Thus, to prepare an enantiomerically pure powder of zeolite
uminated zeolite Y samples55). Highly dealuminated zeolites beta, one would have to synthesize pure polymorph A and then
contain both mesopores and micropores56 and have been one enantiomorph of polymorph A. Raul and I pointed out that
commercialized as catalysts, e.g., the 3DDM (3-dimensional there are frameworks that should have single crystals that are
dealuminated mordenite) catalysts that Dow has commercial- enantiomerically pure (analogous to the dense silica, quartz).1
ized (Dow/Kellogg Process) for the synthesis of cumene. When synthesizing these in powder form, there should be a
These methods of creating hierarchically organized micro- 50−50 mixture of the two enantiomorphs. These structure
porous materials are economically viable for large scale types are likely to be more amenable to creating enantiomeri-
preparation. The size, shape, and number of mesopores are cally pure powders as one would not have to first solve the
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Chemistry of Materials Perspective

problem of obtaining a pure polymorph. Structures of this type can be at low pH and high salt concentrations,71 that were
have been synthesized and are discussed below. previously thought impossible.
In order to obtain a pure sample of a chiral zeolite, chiral This area of science and technology has most certainly been
organic molecules will be needed in the synthesis to direct the driven in the past and will be in the future by the chemistry of
formation of a bulk sample of a pure enantiomorph.1 Several the materials. Because of the uniformity of the materials, the
chiral molecules have been used in the synthesis of zeolites.63 ability to control the molecular-level chemistry and architec-
The question arises as to why the chiral molecules used have tures allows one to design for macroscopic properties by tuning
not led to chiral framework structures. Part of the answer the molecular-level chemistry. Thus, as the chemistry of these
involves the mobility of the organic in the formed inorganic materials (both the synthesis chemistry and the chemistry of
structure. Thus, the use of a rigid organic that fits into the the framework solids) is further elucidated, it will enable
zeolite pore structure without the ability to have any motion investigators to exploit these solids in new ways. In this brief
(even rotational motion of any portion of the molecule) will be Perspective, I have provided my opinions of what I believe are
necessary. some of the most significant areas of investigation. There are
Recently, materials have been synthesized that have other excellent reviews available that cover topics not discussed
enantiomorphs.64−66 First, the germanosilicate material was here (e.g., refs 47, 57, and 72), and I would hope that those
prepared (structure code STW) that has helical pores.64 Since readers interested in the chemistry of zeolite and molecular
sieve materials also obtain those references.

■
germanosilicates do not have the thermal stability of silicates, it
was desirable to prepare the STW structure in silica alone.
Rojas and Camblor synthesized the pure-silica material they AUTHOR INFORMATION
called HPM-1 that has the STW structure.65 This pure-silica Notes
material was prepared using an achiral organic molecule, and The authors declare no competing financial interest.
the individual crystals do contain optical activity.66 However, Biography
the bulk powder must be a racemic mixture of the two Mark E. Davis is the Warren and Katharine Schlinger Professor of
enantiomorphs. It would be quite interesting to perform the Chemical Engineering at the California Institute of Technology. He
synthesis of HPM-1 with chiral organic molecules in the has over 375 scientific publications, two textbooks, and over 50 US
attempt to obtain a single enantiomorph, as separation of the patents. Professor Davis was the first engineer to win the NSF Alan T.
individual chiral crystals into enantiomerically pure powdered Waterman Award. He was elected in the National Academy of
samples is unlikely to be feasible. Engineering in 1997, the National Academy of Sciences in 2006, and
Framework Positioning of Atoms by Design. It is well- the Institute of Medicine of the National Academies in 2011.

■
known that the position of atoms such as aluminum can have
dramatic effects on the properties of the zeolite. For example, ACKNOWLEDGMENTS
only aluminum atoms in small pores of zeolites can be used to I thank my long time collaborator and friend Dr. Stacey Zones
create acid sites that can carbonylate methanol.67 Also, different for helpful discussions. I also thank Urbano Diaz for providing
site distributions of Si and Ga in the zeolite natrolite can me with Figure 4.

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significantly alter the ion exchange properties.68 Therefore, it is
of great scientific and technological interest to create synthetic REFERENCES
methods that would allow for the placement of atoms into
(1) Davis, M. E.; Lobo, R. F. Chem. Mater. 1992, 4, 756−768.
specific crystallographic sites within framework materials. At (2) Zones, S. I. Microporous Mesoporous Mater. 2011, 144, 1−8.
present, there are synthetic efforts aimed at altering the (3) Martínez, C.; Corma, A. Coord. Chem. Rev. 2011, 255, 1558−
framework positioning between large and small cages, and the 1580.
resulting materials have shown interesting catalytic behav- (4) Wright, J. K.; Kalns, J.; Wolf, E. A.; Traweek, F.; Schwarz, S.;
iors.69,70 Ultimately, it would be advantageous to be able to not Loeffler, C. K.; Snyder, W.; Yantis, L. D.; Eggers, J. J. Trauma 2004,
only alter the distribution between pore/cage size areas but 57, 224−230.
create crystallographic site specific synthetic methods. One (5) Neuffer, M. C.; McDivitt, J.; Rose, D.; King, K.; Cloonan, C. C.;
thought that we explored in this territory was the use of Zn as a Vayer, J. S. Mil. Med. 2004, 169, 716−720.
(6) Cunningham, J. Highly selective molecular confinement for the
substitute for Si. Since the Zn−O−Si angle is ca. 130 degrees,
prevention and removal of taint in foods and beverages. U.S. Patent
Zn has a tendency to order into those sites with tighter angles. 7,629,009, December 8, 2009.
While we have been able to produce ordered zincosilicates, we (7) Vignola, R.; Bagatin, R.; D’Auris, A. D. F.; Flego, C.; Nalli, M.;
have thus far been unable to prepare framework materials that Ghisletti, D.; Millini, R.; Sisto, R. Chem. Eng. J. 2011, 178, 204−209.
show good microporosity and stability and have Zn ordered (8) Vignola, R.; Bagatin, R.; D’Auris, A. D. F.; Massara, E. P.;
into specific crystallographic positions. Ghisletti, D.; Millini, R.; Sisto, R. Chem. Eng. J. 2011, 178, 210−216.

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(9) Davis, M. E. Nature 2002, 417, 813−821.
(10) Jiang, J. X.; Yu, J. H.; Corma, A. Angew. Chem., Int. Ed. 2010, 49,
FINAL THOUGHTS 3120−3145.
Zeolites and zeolite-like materials are finding new applications (11) Howard, D. G.; Tschernich, R. W.; Smith, J. V.; Klein, G. L. Am.
as the number of structures and types of compositions of these Mineral. 1990, 75, 1200−1204.
microporous materials continues to expand. The ability to (12) Lobo, R. F.; Pan, M.; Chan, I.; Li, H. X.; Medrud, R. C.; Zones,
control the chemistry of these materials has greatly advanced S. I.; Crozier, P. A.; Davis, M. E. Science 1993, 262, 1543−1546.
(13) Simancas, R.; Dari, D.; Velamazan, N.; Navarro, M. T.; Cantin,
since the time of our 1992 review,1 and it is going to be A.; Sastre, G.; Corma, A.; Rey, F. Science 2010, 330, 1219−1222.
interesting to see what happens in the future. The preparation (14) Wagner, P.; Nakagawa, Y.; Lee, G. S.; Davis, M. E.; Elomari, S.;
of zeolites with new properties, e.g., hydrophobic structures Medrud, R. C.; Zones, S. I. J. Am. Chem. Soc. 2000, 122, 263−273.
containing isolated Lewis acid centers, has opened new (15) Zones, S. I.; Burton, A. W.; Lee, G. S.; Olmstead, M. M. J. Am.
chemistries, e.g., reactions of sugars in aqueous media that Chem. Soc. 2007, 129, 9066−9079.

F dx.doi.org/10.1021/cm401914u | Chem. Mater. XXXX, XXX, XXX−XXX

Chemistry of Materials Perspective

(16) Burton, A. W.; Lee, G. S.; Zones, S. I. Microporous Mesoporous (48) Ramos, F. S. O.; de Pietre, M. K.; Pastore, H. O. RSC Adv. 2013,
Mater. 2006, 90, 129−144. 3, 2084−2111.
(17) Shvets, O. V.; Kasian, N.; Zukal, A.; Pinkas, J.; Cejka, J. Chem. (49) Roth, W. J.; Cejka, J. Catal. Sci. Tech. 2011, 1, 43−53.
Mater. 2010, 22, 3482−3495. (50) Maheshwari, S.; Jordan, E.; Kumar, S.; Bates, F. S.; Penn, R. L.;
(18) Martinez-Franco, R.; Moliner, M.; Yun, Y.; Sun, J.; Wan, W.; Shantz, D. F.; Tsapatsis, M. J. Am. Chem. Soc. 2008, 130, 1507−1516.
Zou, X.; Corma, A. Proc. Natl. Acad. Sci. U.S.A. 2013, 110, 3749−3754. (51) Roth, W. J.; Shvets, O. V.; Shamzhy, M.; Chlubna, P.; Kubu, M.;
(19) Corma, A.; Davis, M. E. ChemPhysChem 2004, 5, 304−313. Nachtigall, P.; Cejka, J. J. Am. Chem. Soc. 2011, 133, 6130−6133.
(20) Blackwell, C. S.; Broach, R. W.; Gatter, M. G.; Holmgren, J. S.; (52) Chlubna, P.; Roth, W. J.; Greer, H. F.; Zhou, W. Z.; Shvets, O.;
Jan, D. Y.; Lewis, G. J.; Mezza, B. J.; Mezza, T. M.; Miller, M. A.; Zukal, A.; Cejka, J.; Morris, R. E. Chem. Mater. 2013, 25, 542−547.
Moscoso, J. G.; Patton, R. L.; Rohde, L. M.; Schoonover, M. W.; (53) Verheyen, E.; Joos, L.; Van Havenbergh, K.; Breynaert, E.;
Sinkler, W.; Wilson, B. A.; Wilson, S. T. Angew. Chem., Int. Ed. 2003, Kasian, N.; Gobechiya, E.; Houthoofd, K.; Martineau, C.; Hinterstein,
42, 1737−1740. M.; Taulelle, F.; Van Speybroeck, V.; Waroquier, M.; Bals, S.; Van
(21) Park, M. B.; Cho, S. J.; Hong, S. B. J. Am. Chem. Soc. 2011, 133, Tendeloo, G.; Kirschhock, C. E. A.; Martens, J. A. Nat. Mater. 2012,
1917−1934. 11, 1059−1064.
(22) Lee, H.; Zones, S. I.; Davis, M. E. Nature 2003, 425, 385−388. (54) Roth, W. J.; Nachtigall, P.; Morris, R. E.; Wheatley, P. S.;
(23) Song, J.; Dai, L.; Ji, Y.; Xiao, F. S. Chem. Mater. 2006, 18, 2775− Seymour, V. R.; Ashbrook, S. E.; Chlubna, P.; Grajciar, L.; Polozij, M.;
2777. Zukal, A.; Shvets, O.; Cejka, J. Nat. Chem. 2013, 5, 628−633.
(24) Xie, B.; Song, J.; Ren, L.; Ji, Y.; Li, J.; Xiao, F. S. Chem. Mater. (55) Janssen, A. H.; Koster, A. J.; de Jong, K. P. J. Phys. Chem. B
2008, 20, 4533−4535. 2002, 106, 11905−11909.
(25) Boggs, R. C.; Howard, D. G.; Smith, J. V.; Klein, G. L. Am. (56) Garces, J. M.; Olken, M. M.; Lee, G. J.; Meima, G. R.; Jacobs, P.
Mineral. 1993, 78, 822−826. A.; Martens, J. A. Top. Catal. 2009, 52, 1175−1181.
(26) Kamimura, Y.; Chaikittisilp, W.; Itabashi, K.; Shimojima, A.; (57) Moliner, M. ISRN Mater. Sci. 2012, 2012, article ID 789525;
Okubo, T. Chem.−Asian J. 2010, 5, 2182−2191. DOI:10:5402/2012/789525.
(27) Itabashi, K.; Kamimura, Y.; Iyoki, K.; Shimojima, A.; Okubo, T. (58) Na, K.; Choi, M.; Ryoo, R. Microporous Mesoporous Mater. 2013,
J. Am. Chem. Soc. 2012, 134, 11542−11549. 166, 3−19.
(28) Kamimura, Y.; Itabashi, K.; Okubo, T. Micropor. Mesopor. Mat. (59) Serrano, D. P.; Escola, J. M.; Pizarro, P. Chem. Soc. Rev. 2013,
2012, 147, 149−156. 42, 4000−4035.
(29) Yokoi, T.; Yoshioka, M.; Ima, H.; Tatsumi, T. Angew. Chem., Int. (60) Chaikittisilp, W.; Suzuki, Y.; Mukti, R. R.; Suzuki, T.; Sugita, K.;
Ed. 2009, 48, 9884−9887. Itabashi, K.; Shimojima, A.; Okubo, T. Angew. Chem., Int. Ed. 2013, 52,
(30) De Baerdemaeker, T.; Yilmaz, B.; Muller, U.; Feyen, M.; Xiao, 3355−3359.
F.-S.; Zhang, W.; Tatsumi, T.; Gies, H.; Bao, X.; De Vos, D. J. Catal., in (61) Zhang, X. Y.; Liu, D. X.; Xu, D. D.; Asahina, S.; Cychosz, K. A.;
press. Agrawal, K. V.; Al Wahedi, Y.; Bhan, A.; Al Hashimi, S.; Terasaki, O.;
(31) Ren, L. M.; Wu, Q. M.; Yang, C. G.; Zhu, L. F.; Li, C. J.; Zhang, Thommes, M.; Tsapatsis, M. Science 2012, 336, 1684−1687.
P. L.; Zhang, H. Y.; Meng, X. J.; Xiao, F. S. J. Am. Chem. Soc. 2012, (62) Xu, D.; Swindlehurst, G. R.; Wu, H.; Olson, D. H.; Zhang, X.;
134, 15173−15176. Tsapatsis, M. Adv. Funct. Mater., in press.
(32) Koller, H.; Lobo, R. F.; Burkett, S. L.; Davis, M. E. J. Phys. Chem. (63) Davis, M. E. Top. Catal. 2003, 25, 3−7.
1995, 99, 12588−12596. (64) Tang, L Q.; Shi, L.; Bonneau, C.; Sun, J. L.; Yue, J. J.; Ojuva, A.;
(33) Eroshenko, V.; Regis, R. C.; Soulard, M.; Patarin, J. C. R. Phys. Lee, B. L.; Kritikos, M.; Bell, R. G.; Bacsik, Z.; Mink, J.; Zou, X. D. Nat.
2002, 3, 111−119. Mater. 2008, 7, 381−385.
(34) Karbowiak, T.; Saada, M. A.; Rigolet, S.; Ballandras, A.; Weber, (65) Rojas, A.; Camblor, M. A. Angew. Chem., Int. Ed. 2012, 51,
G.; Bezverkhyy, I.; Soulard, M.; Patarin, J.; Bellat, J. P. Phys. Chem. 3854−3856.
Chem. Phys. 2010, 12, 11454−11466. (66) Rojas, A.; Arteaga, O.; Kahr, B.; Camblor, M. A. J. Am. Chem.
(35) Moliner, M.; Roman-Leshkov, Y.; Davis, M. E. Proc. Natl. Acad. Soc. 2013, 135, 11975−11984.
Sci. U.S.A. 2010, 107, 6164−6168. (67) Bhan, A.; Iglesia, E. Acc. Chem. Res. 2008, 41, 559−567.
(36) Bermejo-Deval, R.; Assary, R. S.; Nikolla, E.; Moliner, M.; (68) Shin, J.; Bhange, D. S.; Camblor, M. A.; Lee, Y.; Kim, W. J.;
Roman-Leshkov, Y.; Hwang, S. J.; Palsdottir, A.; Silverman, D.; Lobo, Nam, I. S.; Hong, S. B. J. Am. Chem. Soc. 2011, 133, 10587−10598.
R. F.; Curtiss, L. A.; Davis, M. E. Proc. Natl. Acad. Sci. U.S.A. 2012, 109, (69) Pinar, A. B.; Marquez-Alvarez, C.; Grande-Casas, M.; Perez-
9727−9732. Pariente, J. J. Catal. 2009, 263, 258−265.
(37) Roman-Leshkov, Y.; Davis, M. E. ACS Catal. 2011, 1, 1566− (70) Roman-Leshkov, Y.; Moliner, M.; Davis, M. E. J. Phys. Chem. C
1580. 2011, 115, 1096−1102.
(71) Nikolla, E.; Roman-Leshkov, Y.; Moliner, M.; Davis, M. E. ACS
(38) Camblor, M. A.; Villaescusa, L. A.; Diaz-Cabanas, M. J. Top.
Catal. 2011, 1, 408−410.
Catal. 1999, 9, 59−76.
(72) Cejka, J.; Centi, G.; Perez-Pariente, J.; Roth, W. J. Catal. Today
(39) Zones, S. I.; Burton, A. W.; Lee, G. S.; Olmstead, M. M. J. Am.
2012, 179, 2−15.
Chem. Soc. 2007, 129, 9066−9079.
(40) Rojas, A.; Camblor, M. A. Angew. Chem., Int. Ed. 2012, 51,
3854−3856.
(41) Lagaly, G.; Beneke, K.; Kammermeier, H. Naturforsch. Sect. B
1979, 34, 666−674.
(42) Marler, B.; Gies, H. Eur. J. Mineral. 2012, 24, 405−428.
(43) Leonowicz, M. E.; Lawton, J. A.; Lawton, S. L.; Rubin, M. K.
Science 1994, 264, 1910−1913.
(44) Sprung, R.; Davis, M. E.; Kauffman, J. S.; Dybowski, C. Ind. Eng.
Chem. Res. 1990, 29, 213−220.
(45) Corma, A.; Fornes, V.; Pergher, S. B.; Maesen, T. L. M.; Buglass,
J. G. Nature 1998, 396, 353−356.
(46) Kresge, C. T.; Roth, W. J.; Simmons, K. G.; Vartuli, J. C.
Crystalline Oxide Material. U.S. Pat. 5,229,341, July 20, 1993.
(47) Diaz, U. ISRN Chem. Eng. 2012, Article ID 537164, 35 pages;
DOI:10.5402/2012/537164.

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