Studies in Surface Science and Catalysis 157

J. Cejka and H. van Bekkum (Editors) 263

9 2005 Elsevier B.V. All rights reserved.

Advanced applications of zeolites

T. Bein and S. Mintova

Department of Chemistry and Biochemistry, University of Munich, Butenandtstr. 5-13 (E),

81377 Munich, Germany

1. INTRODUCTION
2. ADVANCED APPLICATIONS OF ZEOLITE CRYSTALS AND POWDERS
2.1. Storage materials
2.2. Encapsulation of organic dye molecules
2.3. Zeolite hosts for nanoclusters
2.4. Biological and medical applications
3. ZEOLITE FILMS, LAYERS AND COMPLEX MORPHOLOGIES
3.1. Synthesis of zeolite films and membranes
3.2. Applications of zeolite films
4. CONCLUSIONS
REFERENCES

1. INTRODUCTION

Over the past decade crystalline microporous materials, in particular zeolites, have continued
to find new applications in their traditional areas of use such as catalysis, separation and ion
exchange due to their unique physicochemical properties and improved structuring in
appropriate morphologies.[1,2,3,4,5] The current impact of molecular sieve materials is
significant, with applications ranging from petroleum refining for fuels and petrochemical
processes for various chemicals to air separation and nuclear waste management.
The well-defined porous structure of zeolitic materials makes these materials true shape-
selective molecular sieves. The presence of charge-compensating cations such as alkaline and
alkaline earth cations, protons, etc. within the inorganic frameworks adds ion exchange and
catalytic properties. Moreover, the hydrophobic nature of pure silica zeolites or the
hydrophilic nature of aluminosilicates makes these solids useful as specific adsorbents of
organic molecules or water in the gas or liquid phase.
In addition to the more traditional applications, new applications of these versatile
materials are now being explored by an increasing number of research groups. These
applications often utilize the unique spatial structuring of the zeolite channel system for novel
concepts such as the stabilization of nanoscale forms of matter, size-selective chemical
sensing, or separation of reaction spaces in electron transfer processes, to name just a
few.[6,7] Furthermore, a number of novel applications depends not only on the control of
pore structure and intrazeolite chemistry, but also on the ability to control the external
morphology, for example in thin membranes for separations or in the design of sensor
264

devices. These systems are often excellent examples of our increasing control of the structure
of materials at the nanoscale, using "bottom up" chemical strategies. It is the aim of this
review to present these new developments in zeolite science and to point to successful or
emerging applications in this field.
We have structured the review according to the morphology of the zeolite involved, i.e.,
first we will deal with isolated zeolite crystals or powders, followed by a discussion of zeolite
films, membranes and other more complex morphologies.

2. ADVANCED APPLICATIONS OF ZEOLITE CRYSTALS AND POWDERS

2.1. Storage materials

Hydrogen storage
Hydrogen storage on porous materials has attracted considerable attention because of the
great importance of hydrogen as a potential substitute for fossil fuel. Various methods for
storing hydrogen including gaseous, liquid and solid-state storage based on molecular sieves
have been considered. The particular interest in using zeolite-type materials as gas storage
media is due to the fact that by changing the size and charge of exchangeable cations, the ion-
molecule interactions can be adjusted, and the diameter of the channels can be controlled, thus
enabling the effective trapping of differently sized gas molecules.
The large internal surface area of zeolite Y leads to a relatively high hydrogen uptake. In
hydrogen storage applications, the structures of the host materials play a major role in
achieving reasonable hydrogen adsorption capacities.J8] Synthetic zeolites such as A, Y, X,
mordenite, chabazite, sodalite, gismondine and thomsonite, etc. were used as powder carriers
for hydrogen storage (Fig. 1).

Fig. 1. Framework structures of (a) sodalite, (b) zeolite A, (c) zeolites X and Y, and (d) zeolite RHO.
The comers represent Si or AI and the lines represent oxygen bridges.

One working principle is based on forcing the guest molecules into the cavities of the
molecular sieves at elevated temperatures and pressures, and upon cooling to room
temperature, hydrogen is trapped inside the cavities and could be released again by raising the
temperature.J9] It was found that sodalite could store 9.2 cm3/g (0.082 wt. %) of hydrogen if
loaded at about 300~ and a pressure of 100 bar. However, at very low temperatures, the
storage capacity is found to be 1.2 wt. % (at-196~ Additionally, physical adsorption
at low temperature is significant due to the large specific surface area of the zeolites. The
specific surface area measurements of the zeolites under consideration can be plotted against
 265

hydrogen uptake values (Fig. 2). As expected, the zeolites X and Y offer a maximum
hydrogen storage capacity; these can be considered to be low-cost media for stationary
hydrogen storage applications.[11,12]

1.8. Nj X ~ a y
~ 1.6-
CdX~oCdY

~
= 1.4
o
:= 1.2
0

0.8
i ~
0;7,'
Re= 0.9826
~
0
0.6
t_

"~ 0.4
c-
0.2
oCdRHO
| , w

200 400 600 800

BET surfacearea (m2/g)

Fig. 2. Correlation between hydrogen adsorption at-196 ~ and the BET surface area of different
zeolites. Ref. [12]
A critical re-examination of the sorption properties of carbon nanotubes, filaments and
fibers with respect to H2 storage did not show more than about 1 wt.% uptake of the gas, and
metal-exchanged zeolites have been suggested as alternative candidates for that application.
The reversible storage of molecular hydrogen is critical for large-scale applications of
hydrogen as fuel, in particular for mobile applications. In zeolites where Si atoms can be
substituted by A1 atoms, metal cations act as charge-balancing ions of the negatively charged
framework by coordinating to the lattice oxygen atoms such that their electronic properties
can experience changes that ultimately could affect their interactions with H2
molecules.J13,14] These changes vary depending on the coordination environment of the
metals, thus resulting in very different abilities of cations in different zeolite coordination
sites for binding hydrogen.[ 15]
The molecular sieves can also be used as storage medium for ammonia.[16] The
ammonia adsorption capacity of zeolites has been increased substantially by ion exchange
with transition metal ions due to the increase in the number of ammonia adsorption sites. The
ammonia adsorption capacity of zeolite Y (FAU structure) with Co and Cu was higher than
that of Na-Y; on the other hand the adsorption on K-Y, Rb-Y and Cs-Y was lower than on
Na-Y due to the decrease of electrostatic attraction between ammonia and the zeolite surface.

Methane storage
Alternative fuels should be substantially non-petroleum in order to provide energy
security and environmental benefits, and to substitute for conventional fuels such as gasoline
and diesel. Natural gas consisting mainly of methane fits this definition, and the natural gas is
mainly stored as compressed natural gas in pressure vessels or as adsorbed gas that can be
stored in a porous solid at a low pressure. An important advantage of zeolites over activated
266

carbon is their high crystallinity, a large accessible surface area with a high free volume, a
low framework density and relatively strong interactions between the framework and the
methane molecules.[ 17]

Storage of heat
Zeolites are attractive for the possible use in heating and cooling systems which utilize
solar energy as a heat source (Fig. 3). When heated, zeolites release water vapor and as long
as they stay dry, they can store large amounts of "latent" heat. When zeolites absorb
moisture, they release the stored heat, and this regenerative cycle can be repeated numerous
times.

Fig. 3. Heating and cooling systems based on highly hydrophilic zeolites using solar energy as a heat
source.

Thermochemical storage based on sorption/desorption of water in porous materials

appears to be suitable for seasonal storage in so-called low energy houses. In this application
one aims for materials with a high sorption capacity towards water. The relationships between
the composition and the structure of zeolites upon modification and the sorption/desorption
properties of water such as the sorption capacity, the heat of sorption, and the desorption
temperature are the most important parameters for solar applications. The standard procedures
used for the modification of the zeolites for this application include ion exchange of Na with
Li, Ca, Mg, Zn, Co, A1, Fe or additional impregnation of the porous hosts with hygroscopic
salts such as MgCI2 and CaCI2. The replacement of two monovalent sodium ions by one
bivalent magnesium ion for charge compensation can enlarge the pore volume of the zeolite,
and consequently, provide more space for the adsorption of the water molecules in the pores,
which increases the potential to store more energy. In this case the water is more strongly
bonded to the bivalent ions with their higher charge density. However, high heats of
adsorption also imply higher temperatures for desorption of the water from the zeolites.[18]
An arrangement involving zeolite coatings synthesized on metal gauzes was applied in order
to remove limitations originating from the existence of temperature and condensation
gradients within the solar collector.[19]

2.2. Encapsulation of organic dye molecules

The nanosized void spaces in zeolites have been exploited to serve as hosts for
interesting organic guest molecules. A large variety of organic dye molecules have been
incorporated in the defined cages and channels of uniform size of the zeolites. Control of the
morphology and the size of zeolite hosts allow for the optimisation of the dye-zeolite
composites for a specific application.[20]
 267

Large crystals, mainly with the one-dimensional AFI type channel structure (AIPO4-5),
have been used for studying the optical properties of the dye-zeolite composites by means of
optical microscopy,[21,22,23,24] while small crystals are of interest for high-efficiency
photonic antennae. Furthermore, nanosized dye-loaded crystals have been used for the
generation of dye-sensitized solar cells, light emitting nanocomposites, as well as fluorescent
probes in cell biology and in analytical chemistry (Fig. 4).[25] These materials exhibit great
stability against chemical attack, photobleaching and thermal decomposition. For example,
zeolite LTL has been synthesized in a large range of sizes (30 nm up to 3000 nm) by changing
the composition of the starting precursor solutions and reaction conditions.[26] The
morphology, pore volume and the size distribution of zeolite nanocrystals strongly affect the
behaviour of optical antenna host-guest systems for light harvesting and energy transport.

Fig. 4. a) Schematic representation of zeolite with donor molecule modified with acceptor stopcocks
and b) magnification showing details of zeolite channel and the shape of the stopcock molecule. Ref.
25b

Another interesting example among the many uses of porous solids as a host material is
the zeolite-dye microlaser, where the incorporation of organic dyes as guest species in
microporous crystalline A1PO4-5 gave the first lasing molecular sieve with the size, shape and
arrangement of the porous crystals affecting the performance of the system.[27] Organic dye
guest molecules such as 1-ethyl-4-[4-(p-dimethylaminophenyl)-l,3-butadienyl]-pyridinium
perchlorate were inserted into the 0.73-nm-wide channel pores of a zeolite A1PO4-5 host. The
dye molecules were not only aligned along the host channel axis but also they have been
oriented (Fig. 5).

..... Ho2N ,oH:oH,2 N,OH3 2 "

c~o4

Fig. 5. Dye moleculel-ethyl-4-[4-(p-dimethylaminophenyl)- 1,3-butadienyl]-pyridinium perchlorate

inserted in the one-dimensional channel of AIPO-5 molecular sieve. Ref. 27b
268

The substantial increase in the stability of organic dyes in zeolites opens the possibility to
prepare new pigments with a large variety of colours via combination of two or more dyes.
For a recent review on the incorporation of dyes in zeolites see ref. [28]. Zeolites appear to be
a promising starting material for the synthesis of ultramarine analogues.[29] It has been
found that the structures of SOD, LTA and FAU containing high aluminium levels were the
most suitable for the synthesis. The main advantage of zeolites and polysulphides applied for
the preparation of ultramarine consisted in a substantial reduction of volatile sulphur
compounds upon calcination. The colour of the samples can be modified markedly by using
different polysulphides and by altering the conditions for hydrothermal and post-synthesis
treatments. The latter affect the oxidation state of the sulphur species.
Different stages of organization have been accomplished ranging from the spatial
arrangements of dyes in the zeolite channels to the specific adsorption of molecules at the
channel entrances as well as coupling of the dye-zeolite crystals to external devices. In most
of the cases zeolites with LTA, FAU, MFI, AFI and LTL type structures have been used for
these supramolecular assemblies.
The dye 2-(2'-hydroxyphenyl)benzothiazole (HBT) was successfully incorporated into
the voids of nanosized FAU-type zeolite through a hydrothermal treatment of colloidal
precursor solutions. The photoconversion from the keto to the enol form of the HBT molecule
incorporated in the HBT-FAU sample upon UV excitation at 385 nm is shown in Fig. 6.[30]
This work demonstrates, with HBT as an example, the great potential presented by nanoscale
zeolites stabilized in solutions for developing host/guest systems with medium-size organic
molecules where optical in-situ investigations of ultrafast photochemical processes are
possible. The combination of nanosized porous hosts containing organic compounds such as
dyes or photochromic molecules and ultrafast spectroscopy opens new perspectives for the
development of nanoscale devices.

HBT-FAU
0,75 irradiation @ 3 8 5 n m
0.5 min
1 min
0,50 2 min
CI "~-xk ~ 4 min
O
0,25

0,00
300 350 ' 4()0 ' 450 ' 51J0
;L (nm)

Fig. 6. Changes of the absorption in sample HBT-FAU upon excitation at 385 nm. [30]
 269

2.3. Zeolite hosts for nanoclusters

Metal clusters
The importance of small metal clusters in catalysis and in many advanced applications is
due to the significant physical changes that occur when reducing the size of a material down
to a few nanometers; these systems often display unique nanochemical and nanophysical
properties and allow the creation of nanoscopic magnets, spatially ordered nanostructures,
nano-electronic devices, quantum electronics, etc.
The stringent requirements for novel optical and electronic materials with precise
nanoparticle size, geometry, and dimensionality are stimulating research efforts aimed at the
formation of metal nanoclusters in confined matrices such as polymers, micro- and
mesoporous materials. Metal nanoclusters or nanowires can be prepared in confined spaces by
using the internal structures of micro- and mesoporous hosts. The size and the shape of the
pore opening could determine the properties of the metal nanostructures. In Fig. 7 we give
three examples where Ag nanoclusters are formed in partially exchanged zeolite A, a silver
network is formed in highly silver-exchanged crystals, while nanowires are formed in a one-
dimensional mesoporous matrix.
In recent years, molecular sieves have found new uses as hosts for the preparation of
small metal- and semiconductor clusters that can be grown in confined zeolite spaces and are
envisioned for uses in photo-catalysis, non-linear optics, sensors, flat panel displays, etc..[31]
The framework-type structures of zeolites can be described with the presence of the n- rings,
e.g., 4-, 6-, 8-, 12-rings or double 5-, 6-, 8- rings, or secondary building units, e.g. the sodalite
cavity, super cages, and others. These confined spaces can be used for the preparation of
optical and electronic materials with desired properties.

Fig. 7. Schematic representation of ordered Ag nanostructures formed as (a) nanoclusters in LTA

zeolite, (b) spatial network in LTA, and (c) wires in a mesoporous matrix.

Optical spectroscopy is being used for the characterization of the quantum electronic
state of nanoscale materials, particularly alkali metal clusters incorporated in the space of
zeolite crystals. For example, potassium clusters were incorporated into cage-type LTA and
channel-type MOR zeolites that demonstrated even ferromagnetism at low temperatures.[32]
The LTA framework is constructed of 13-cages interconnected with double 4-rings among
which the or-cages are formed. The latter are connected via 8-membered rings having a size of
4.1 A. The effective inner diameter of the cages depends on the size of the cations, and it is
about 11 A and 7 /~ for the a-cages and 13-cages, respectively. In the case of MOR-type
zeolite, there are two types of elliptical channels with size of 6.5 x 7.0 A and 2.6 x 5.7 A
called main and sub-channels, respectively. When the alkali metals are adsorbed in the
dehydrated zeolites, different types of cationic clusters are generated in the free spaces.
Ferromagnetism has been observed in the zeolites with a medium loading density of K
270

although no magnetic elements are present- this effect was attributed to the inter-cluster
interactions.
The dynamics and the local environment of silver cations in different types of zeolites
during hydration/dehydration/rehydration cycles can be followed with optical methods. The
size of metallic clusters in zeolites is controlled by the position of the preferential adsorption
of silver cations in the zeolite framework. A colour change from white to orange is due to a
decreased number of water ligands coordinated to the silver cations.[33] Silver clusters have
been prepared in various zeolite hosts, mainly in LTA, LTL, MFI, FAU, and MOR via
impregnation, ion exchange, diffusion at elevated temperatures, and spontaneous monolayer
dispersion. The quantum confinement effect of the zeolite channels endows these host-guest
nanocomposites with interesting optical properties.
Metal clusters in general have been prepared in the cavities and channels of zeolites A,
X, Y, chabazite, mordenite, etc., by vacuum dehydration, by reduction with reducing agents,
or by X-ray or gamma-irradiation. The most-studied Ag- and Cu- clusters were prepared from
various types of molecular precursors, while Au clusters have been less studied because the
gold ions are unstable and must be stabilized by specific ligands.[34] Gold-loaded zeolites
have been used as catalysts for removing harmful materials such a NO, CO, etc.
Photoconductors
The nanocomposite materials of FAU-AgI and MFI-AgI with high guest-contents in the
form of quantum wires or three-dimensional nanocrystals exhibit optical properties different
from quantum dots. In addition, silver-modified zeolites and silver halide encapsulated
zeolites offer potential applications as fast-ion conductors, information storage materials, or
photoconductors.
The properties of (Ag2S)n clusters formed in zeolite A hosts depend on the amount of
guest, and up to a loading of 4 Ag § per a-cage, the properties of the material are mainly
determined by the presence of isolated clusters and by short-range interactions.[35] The
photoluminescence spectra of (Ag2S)n zeolite composites contain two bands, one around 480
nm (blue-green) and the other at 600 nm (orange-red); the former was observed in samples
with low concentration while the latter dominates the spectra at high silver sulphide content.
The luminescence bands were assigned to (Ag2S), monomers (n = 1, blue-green) and AgaS2
(orange-red), where energy transfer between the Ag2S-donor and Ag4S2-acceptor was
proposed.[36,37] Another interesting property of the luminescence of (Ag2S)n zeolite
composites relates to its distinct temperature dependence, where the orange-red emission
shows stronger quenching with increasing temperature. These samples can be employed in
thermometry applications by observing the luminescence colour and intensity and the
luminescence lifetime. A great advantage of such device is that a contact with an electric
device is not required. The performance of semiconductor clusters in sensing and
thermometry applications does not rely on the high level of organization that is required for
optoelectronic devices.[38]
Semiconductors
CdS, PbS, CdSe, and ZnS clusters are the semiconductor compounds studied most
extensively in zeolites.[39,40] In addition, ternary systems such as ZnCdS have attracted the
interest of many researchers.[41 ] An ordered array of cadmium clusters assembled in zeolite
A was prepared in an attempt to produce heavy metal clusters with different distributions and
geometries.[42] (Fig. 8)
 271

Fig. 8. Cadmium cluster (Cd98§ in the sodalite cage of zeolite A. Ref. [43]

The samples were quite stable under the electron beam and their images are consistent
with a cubic array of high nuclearity clusters occupying most of the sodalite cages, separated
by nearly empty or-cages. However, Cd clusters located not only in the sodalite cages but also
in the 8-rings of zeolites result in different properties.[43]
Sub-nanometric Co-clusters have been produced in MFI and BEA hosts demonstrating
superparamagnetic-paramagnetic phase transitions. Regarding the magnetic properties, a
similar behaviour is observed with the two zeolites, with a large magnetic moment for the
samples with high Co content. The most remarkable property of these materials is a change in
the magnetic behaviour without structural modification under variation of the temperature. At
10 K, the materials behave as typical superparamagnetic nanoparticles, while at 300 K they
behave as pure paramagnetic materials. This property may open the possibility for using
these materials as temperature-dependent magnetic switches.[44,45,46]

Supercapacitors
Nanostructured electrode materials have attracted great interest as a basis for
supercapacitor charge storage devices, as they show better discharging rates and higher
capacities than traditional materials, where the distance within the material over which
electrolyte must transport ions is dramatically smaller than with conventional electrodes
composed of chemically similar bulk materials. In addition, larger surface areas in these
materials can lead to higher currents during charge and discharge compared with conventional
electrodes. From a materials point of view, there are three main categories of electrochemical
capacitors: carbon/carbon, metal oxides and electronically conductive polymers.[47]
Microporous frameworks might offer alternative electrode materials with promising
characteristics and performance, for example ultra-stable Co-containing zeolite Y.[48] The
zeolite Y was used as a high-surface area template on which a redox-active Co(OH)2
nanostructure was synthesized through ion exchange, chemical precipitaton, and self-directed
growth processes. During the ion-exchange reaction, Co 2§ ions undergo exchange with H §
ions to balance the charge of the negatively charged A104 tetrahedral units embedded in the
structure; the zeolite host causes a concentration gradient of Co 2+ ions decreasing from the
272

surface of the USY particles towards the surrounding solution, and forming whisker-type
Co(OH)2. The loosely packed nanometer-scale whiskers create electrochemical accessibility
for electrolyte OH- ions and a fast diffusion rate through the bulk Co(OH)2, which is of
fundamental importance for materials intended for supercapacitor applications.

2.4. Biological and medical applications

The diverse and highly controlled properties of zeolites make them interesting candidates
for a variety of biological and medical applications. Zeolites have been applied to regenerate
artificial dialysis solutions.[49] Another promising application is diagnostic magnetic
resonance imaging (MRI), which relies on administering contrast agents. The contrast agents
contain high-spin metals that bind water molecules and thereby yield proton spin relaxation
times that are orders of magnitude faster than those obtained with free water. Gadolinium
ions, Gd 3§ perform particularly well as contrast agents, but cannot be administered directly
owing to their inherent toxicity. Zeolites with enclosed transition and rare earth metal ions are
being envisioned as contrast agents for the gastrointestinal tract.[50] The zeolite immobilizes
the Gd 3§ and thus mitigates its toxicity (zeolites themselves are not toxic when introduced into
the gastrointestinal tract), while still allowing dynamic coordination of water.
Many proteins that are removed from biological structural matrices become very
unstable. Protein stabilization by binding to the external surface of zeolites is therefore being
investigated. The proteins tend to bind well at or around their isoelectric point to zeolite
particles with high silica content suggesting that the hydrophobicity and the three-dimensional
structures of zeolites have the strongest impact on adsorption. In order to utilize zeolites as
potential chromatographic carriers, it is important that the proteins adsorbed on zeolites must
be recovered easily and the recovered proteins must have the same activities as before. For
example, lysozyme activity has been preserved when using zeolite beta as a carrier.
Moreover, the zeolite carriers are resistant to extreme pH, high and low temperatures,
denaturant, and detergents.[51 ]
The molecular sieves ITQ-1 and ITQ-6 with low aluminum content have been used as
supports for enzyme immobilization; the zeolites exhibit a very ordered external surface and
good thermal stability. Different enzymes including Penicillin G acylase were stabilized via
electrostatic and covalent interactions on zeolite carriers. The possibility of using molecular
sieves for processes involving enzymes as catalysts or sensors has been demonstrated.[52]
Zeolites have also been used as absorbers for perfluorocarbons (PFC), which are applied
in the treatment of respiratory diseases, to control the PFC content in breathing gases.[53] By
preventing water condensation in the zeolite and PFC condensation, the weight gain of the
zeolite absorber over time allows precise measurements with volume errors less than 1% for
PFC volumes grater than 1 ml.
Molecular sieves are used in various applications in nuclear medicine. For example,
small beads of zeolites were soaked in a solution of radioactive ions. These zeolite beads are
employed as point source markers for the identification of anatomical landmarks and for
gamma camera uniformity. Due to their small size and relatively high uptake they provide
excellent devices for measuring spatial resolution, detector uniformity and energy
resolution.[54] Zeolites are also utilized as binding agents for toxic compounds and
antioxidant for selenium, vitamins, and provitamins, and are also used as mineral additive in
various dietary strategies.[55]
Zeolites can be very effective as a vehicle for transferring foreign compounds into a
living cell by optical manipulation.[56] Zeolite particles can hold foreign chemicals in their
fine pores. One example is based on the transport of a zeolite particle doped with a
 273

fluorescent dye into a protoplast cell, and when the particle is delivered the emission from the
dye complexed with intracellular calcium ion is observed. On the other hand, optically driven
transport has great potential since the necessary laser manipulation is remotely controllable.
In the examples given above, the bioactive molecules were adsorbed on the outer surface of
the zeolites.
Important other applications of zeolites in this area include CO2 removal in the breathing
atmosphere in space, and recycling of wastewater. Recently the NASA conducted research on
the removal of gas components under ultra clean room conditions in satellite systems, where
zeolites can reduce the outgassing rate inside of instruments and absorb molecules without
producing additional particles by themselves.

3. Z E O L I T E FILMS, LAYERS AND COMPLEX M O R P H O L O G I E S

3.1. Synthesis of zeolite films and membranes

A number of novel applications of zeolites depend on the ability to create thin, adhesive
films on various substrates. While zeolite films or layers are commonly prepared on dense
substrates such as silicon wafers, zeolite membranes are made on porous supports in order to
permit permeation through the zeolite layer. Numerous synthetic studies have addressed the
goal of obtaining adhesive layers of zeolites on various substrates such as noble and non-
noble metals, glass, ceramics, silicon, and even biological substrates such as cellulose fibers.
For a more detailed discussion of zeolite membranes the reader is referred to the article by
Julbe in this book. Pertinent reviews to this subject are given in the following
references.[57,58]

3.1.1. Synthesis of zeolite films by in situ crystallization

In the synthesis by in situ crystallization, the zeolite crystals grow directly from a
synthetic solution on the surface of an appropriate substrate such as silicon.
For example, continuous multilayered ZSM-5 films were grown on cordierite
modules.[59] Similar films were generated on as-prepared and acid-treated honeycomb
substrates.[60] The latter treatments led to silica-rich surface layers; their composition
affected the Si/A1 ratios of the zeolites crystallized on the cordierite. Thin, defect-free MFI-
type films were also made on porous alpha-alumina and yttria-doped zirconia substrates using
tetrapropylammonium hydroxide (TPAOH) as a structure-directing agent.[61]
Porous materials can also be coated with zeolite films by direct synthesis. For example,
microcellular SiOC ceramic foams in the form of monoliths were coated on their cell walls
with thin films of silicalite-1 and ZSM-5 using a concentrated precursor solution for in situ
hydrothermal growth (Fig. 9).[62] The zeolite-coated monoliths show a bimodal pore system
and are thermally stable to at least 600 ~ A related strategy is based on the conversion of
macroporous Vycor borosilicate glass beads, having pores of about 100 nm, to MFI-type
zeolite-containing beads retaining the same macroscopic shape.[63] This conversion was
achieved by hydrothermal treatment with an aluminium source and a template such as TPABr.

3.1.2. Synthesis of zeolite films by seeded growth

In a second approach for thin film synthesis, a layer of pre-synthesized seed crystals is
deposited on the substrate, followed by some means of binding it to the surface and
subsequent hydrothermal synthesis of the desired zeolite film on the seed layer. This and the
previous growth technique are advantageous if a very strong bond to the substrate is desired.
Furthermore, for a select group of zeolites it has been shown that substantial crystal
274

intergrowth can occur during film synthesis such that the resulting film becomes a dense
zeolite phase that can even be gas-tight. As tightness is a key factor for zeolite membranes,
the above growth techniques have also become the most important methods for membrane
preparation.

Fig. 9. SEM images of the fracture surface of SiOC microcellular foam coated with silicalite-I
crystals synthesized at 150 ~ (a, b) and 125 ~ (c, d).[62]

Thin layers of oriented (with their (h00) faces parallel to the substrate) zeolite A crystals
were prepared by adsorption on oppositely charged substrates by electrostatic attraction.[64]
A silylation reaction was used to modify the external surface of the negatively charged
zeolites such that they exhibited a positive zeta potential. An alternative slow dip-coating
process on substrates bearing the same charge as the zeolites resulted in highly ordered, close-
packed hexagonal colloidal crystals. Such films could also be used as seed layers for
secondary growth, first by local epitaxy on the seed layer and later by incorporating particles
from solution.
A detailed study of the growth process and the structural evolution of silicalite-1 (MFI)
films was undertaken with the aid of grazing incidence synchrotron X-ray diffraction.[65] The
diffraction data of the adsorbed and grown zeolite films at different incident and exit angles
reflect the distribution of the crystal orientation along the film thickness. The films were
prepared via assisted adsorption of nanoscale MFI seed crystals, followed by calcination and
subsequent hydrothermal synthesis on the seed layers. The adsorbed (multi-) layer of seed
crystals consists of randomly oriented crystals. With progressing hydrothermal growth, the
film surface becomes smoother and a preferred crystal orientation with the b-axis close to
vertical to the substrate develops.

3.1.3. Synthesis of zeolite films by vapourphase transport

A third approach, sometimes called vapour transport synthesis, usually relies on the
deposition of a gel-layer on the substrate followed by treatment with a (humid) vapour of
some agents missing in the synthesis mixture, for example a volatile amine, resulting in the
crystallization of the desired zeolite film.
One approach deals with the formation of zeolite ZSM-5 or silicalite-1 from dry
precursor material (dried alumino/silicate gels) via a gas phase transport process in the
 275

presence of dry ammonium fluoride and tetrapropylammonium bromide.[66,67] The authors

suggest that silicon tetrafluoride might act as a mobile species for mass transfer between the
amorphous precursor and the zeolite crystals formed.
The vapour-phase transport method was also successfully used for the preparation of
membranes and bulk material of the following zeolites: MCM-22 membrane (used for the
alkylation of toluene with MeOH to p-xylene),[68] FER-membrane (for the separation of
benzene/p-xylene),[69] EMT crystals using a crown ether as structure-directing agent, J70]
and zeolite beta (BEA).[71] In the latter two examples, a conversion of agglomerated
nanoparticles to highly crystalline zeolite was observed.
A reversed approach using a volatile Si-source (tetraethoxysilane, TEOS) was applied to
prepare MFI membranes by wetting a porous alumina substrate with TPAOH-solution and
exposing it to vapors of TEOS at elevated temperatures.[72] In this case the TEOS must
hydrolyze and gel in situ in the thin liquid film on the porous substrate.

3.1.4. Deposition of zeolite films by laser ablation

It has been shown that pulsed UV-lasers can be used to ablate certain fragments from a
zeolite target; these fragments can be deposited on a substrate and subjected to a subsequent
hydrothermal treatment resulting in crystalline zeolite layers. The initially deposited layers
appear to be X-ray amorphous, although they can still be used to nucleate crystals of the
original zeolite target material. [73,74,75]
In some cases the subsequent hydrothermal growth of the target zeolite results in
preferential crystal alignment in the films. For example, oriented UTD-1 membranes were
obtained via laser ablation from UTD-1 zeolite and deposition on silicon or porous stainless
steel, followed by hydrothermal treatment (Fig. 10).[76] The resulting films showed densely
packed plank-like crystals of UTD-1 with the large one-dimensional pore system oriented
away from the substrate.

Fig. 10. SEM images of a UTD-I film obtained by laser ablation followed by hydrothermal growth
for 72 h. [76]

3.1.5. Deposition of zeolite films from pre-synthesized crystals and growth on molecular
layers
If the demands for tightness of the films are less stringent or irrelevant, other methods
can be used for the formation of zeolite films. Spin-coating of zeolite suspensions (with
nanoscale zeolite crystals) as well as molecular assembly of pre-synthesized zeolite crystals
are viable methods for the deposition of rather smooth films. Furthermore, electrophoresis
was successfully used to attach zeolite crystals to electrically conducting substrates.
276

The molecular assembly of zeolite layers has been developed in an elegant series of
studies by the group of Yoon. In one of their earlier papers, fullerene (C60) was used as a
covalent linker for the attachment of cubic zeolite A (LTA) crystals and ZSM-5 crystals on
glass. This was achieved by tethering (3-aminopropyl)triethoxysilane on the glass surface,
and attaching a layer of fullerene molecules by addition of the terminal amino groups to
fullerene double bonds.[77] The zeolite crystals were separately treated with (3-
aminopropyl)triethoxysilane on their external surface and were allowed to react with the
fullerene-covered surface, thus forming a rather close-packed zeolite monolayer.
Other binding modes for zeolite monolayers include diisocyanates (they readily react
with surface hydroxyl groups on glass or on the zeolite crystals by forming urethane
linkages),[78] 3-halopropylsilyl groups,[79] the reaction between tethered epoxy-groups and
primary amines,[80] and hydrogen bonding. As an example of the latter, the adenine-thymine
binding pair was used to bind thymine-tethered ZSM-5 or zeolite A crystals to adenine-
tethered glass substrates (Fig. 11).[81 ]

Fig. 1I. Scheme for the attachment of zeolite crystals by thymine/adenine-mediated hydrogen-bonding
(left). The thymine and the adenine were tethered to the respective surfaces through l l-
trimethoxysilyl-n-undecyl-linkers. [81] SEM image of a monolayer of cubic thymine-zeolite-A
crystals assembled on adenine-glass at 50 ~ (right).

Well-defined zeolite layers can also be prepared via synthesis in the presence of
molecular or polymeric templates. Some of the first examples in this regard were the
syntheses of porous aluminophosphate and zincophosphate crystals on molecular layers of
alkylphosphonic acids.[82,83] In extending this general templating approach to polymers, a
recent study shows that uniformly aligned polyurethane films turn out to be excellent
templates for the synthesis of well-aligned two-dimensional arrays of silicalite-1 crystals.[84]
It is possible to extend the assembly techniques for zeolite layers to three-dimensional
bodies. For example, the layer-by-layer deposition of a variety of zeolites such as LTA and
BEA on negatively charged polystyrene beads was achieved by first modifying the bead to
adsorb the zeolite particles, followed by the electrostatic layer-by-layer assembly of
alternating zeolite and polyelectrolyte layers of opposite charges (Fig. 12).[85]
 277

Fig. 12. Presentation of the layer-by-layer technique used for the construction of multilayer zeolite
coatings on spheres. [85]

Electrophoresis
An electric field can be used to move charged particles onto a surface, thus resulting in a
thin film. This approach has been used for the deposition of zeolite films on conducting
surfaces. For example, films of zeolites NaA, NaY, and H-ZSM-5 were electrophoretically
deposited from solvents such as acetonitrile and acetone on bodies of various shapes- in this
study an important ingredient was the addition of colloidal silica as a binder that was used to
strengthen the films upon heating to 400 ~ Hydrothermal growth can be used to further
enhance the stability of the resulting zeolite films.[87]

3.2. Applications of zeolite films

We develop the different types of applications based on their underlying physical principles.
As mentioned above, for a discussion of zeolite membranes (see, e.g., [88,89,90]) the reader
should consult the chapter by Julbe in this book.

3.2. I. Electrochemistry with zeolite-coated electrodes

Based on their regular pore structure, it should be possible to impart the molecular
sieving capabilities of zeolites on the surface of electrodes in electrochemical reactions.
Several research groups have addressed this issue by (i) developing ways to modify electrodes
with thin zeolite films and (ii) by studying the resulting changes in electrode behaviour in
electrochemical reactions. The subject has been reviewed.[91]
Mechanically stable faujasite-type films were grown hydrothermally on glassy carbon
electrodes at low temperature.[92] The authors succeeded in demonstrating charge- and size-
278

selectivities of such films (given a sufficient thickness) for redox reactions of model systems
such as Ru(NH3)63+, Fe(CN)63, Ru(bpy)32+, dopamine, and ascorbic acid.
Zeolite films were also explored for their use in potentiometric reactions.[93] The
authors determined the potentiometric response of zeolite-modified electrodes towards cations
in aqueous phase. Three different preparation routes were used for the formation of the zeolite
films; zeolites Y (FAU), A (ETA) and mordenite (MOR) were pressed into discs, sodalite
(SOD) was grown in a free-standing membrane, and for the pressed discs of LTA a secondary
growth phase was added in order to heal defects in the pressed discs. The authors could
demonstrate size-selective behaviour in these systems, i.e., cations with diameters exceeding
those of the zeolite window openings resulted in no detectable potential response.
The various tunable properties of zeolites have inspired a great variety of concepts in
electrochemistry with zeolite-modified electrodes. For example, silver ions inside the zeolite
pore system are not electrochemically active in amperometric detection. However, indirect
analyte detection can occur when the analyte causes the removal of silver ions into the
solution where they are electrochemically detected.[94] This indirect approach was extended
to different copper-exchanged zeolites and demonstrated for the detection of several non-
electroactive ions including alkali metal, ammonium and calcium.[95] A zeolite-modified
electrode (ZME) with high selectivity towards Pb over Cd in cyclic voltammetry was
prepared via electrophoretic deposition of zeolite Y, coated with Nation.[96]
Electrodes modified with zeolites and mesoporous periodic aluminosilicate (MCM-41)
were used for the investigation of encapsulated polyacetylene and polypropyne obtained by in
situ polymerization of the respective monomers on Ni(II) exchanged hosts.[97] The authors
observed high charge uptake during (irreversible) oxidation of the polymers.
The reduction of methylviologen dications to the cation-radicals at ZME (zeolite Y)
interfaces shows a concentration overpotential due to the ion exchange equilibrium with
sodium at the zeolite-solution interface.[98,99] In the process, methylviologen dications
diffuse from the zeolite channels into solution. The authors suggest that ion exchange
accounts for the electron transport mechanism.
A striking example of molecular sieving in a stable, continuous b-oriented silicalite-1
film (having pores of about 0.55 nm) on an electrode was recently demonstrated with redox
probe molecules of different sizes (Fig. 13).[100] Specifically, the smaller complex
Ru(NH3)63+ with a diameter of ca. 0.5 nm was shown to travel through the film, while the
larger complex Co(phen)3 z+ with a diameter of ca. 1.3 nm was completely excluded from the
zeolite film and thus from redox processes.

3.2.2. Zeolite films as dielectric layers for semiconductor applications

In the relentless quest for ever faster computer circuitry, the dielectric constant of the
insulating layers between conductors on the chip is becoming a major issue. This constant
should be as small as possible while the mechanical properties of the dielectric material must
withstand the subsequent processing steps and ensure the integrity of the computer
microprocessor. Nanoscale zeolite crystals, particularly pure silica zeolites, have been
proposed as candidates for thin films with low dielectric constant (low k). As an example,
suspensions of nanoscale crystals of the pure zeolite silicalite-1 (MFI-type) were used for
spin-on deposition of thin dielectric layers.[101 ] The as-deposited films were subsequently
calcined at 450 ~ in order to remove organic molecules and to consolidate the films. The
authors report low dielectric constants (although the adsorption of humidity must be
controlled) and satisfactory mechanical properties of their films.
 279

Films from the same research group were subsequently characterized with regards to their
porosity, showing both zeolite microporosity and textural mesoporosity.[102] The above
concept can be extended towards films with different binders, including organic polymers.
Thus, two-component films comprised of nanoscale silicalite-1 and acrylic latex were
deposited on silicon wafers via spin-coating.[103] In this case, a purified suspension of
colloidal zeolites with sizes of 30 or 60 nm were first deposited followed by calcination. In a
second step, a layer of acrylic latex was deposited, resulting in layers with dielectric constants
between 2.0 and 2.5.

Fig. 13. Structure and concept of size-selective zeolite-coated electrode. (a) Electron micrograph of b-
oriented silicalite-1 film (top view), (b) side view, (c) schematic illustration of molecular sieving of
electro-active species having different sizes. [100]

The dielectric constant of a film of nanozeolites can be reduced further if the volume
fraction of the zeolite is reduced. This was demonstrated by adding a porogen, i.e., gamma-
cyclodextrin, into an MFI-nanoparticle suspension used for spin-coating the film.[104] The
resulting films still had an elastic modulus of about 14 GPa and a dielectric constant of 1.8
after calcination.
The most stable, adhesive and hydrophobic silicalite-1 films can be obtained by in situ
crystallization on the silicon substrate, followed by calcination to remove the organic
template.[105] Their elastic modulus reaches 30-40 GPa, but the dielectric constant was
measured to be 2.7-3.3. These findings suggest an inverse relationship between the
mechanical strength of the films and the lowest achievable dielectric constant.

3.2.3. Optical applications of zeolite films

So far, only few studies have been reported on the use of porous zeolite films for optical
applications. While significant efforts have been extended towards the encapsulation of
various dye molecules into zeolite crystals or powders (see section 2.2), integration of such
systems into thin films has not been pursued by many groups yet. As one of the few examples
reported so far, we discuss the inclusion of oriented hemicyanine dyes into thin zeolite films
aimed at Second Harmonic Generation (SHG).[106] The zeolite film plays the important role
280

of organizing the orientation of the optically active molecules. Thus, silicalite-1 films with a
thickness of 400 nm were prepared on glass plates, and hemicyanine dyes with different alkyl
chain lengths (between 3 and 24 carbon atoms) were incorporated into the film via diffusion
from a methanolic solution. It was concluded from the optical data that the dyes form only a
small average tilt angle of about 8 degrees with respect to the channels of the zeolite host. The
high degree of uniform alignment in these films (albeit at low dye densities) is being viewed
as a promising feature for the future design of host-guest films for nonlinear optical
applications.
Photocatalytic reactions in heterogeneous media rely on efficient energy transfer to the
reacting molecules- this calls for effectively reducing the scattering at interfaces. One
possible strategy for achieving this relies on the use of nanoscale zeolites in thin films. For
example, the photocatalytic isomerization of cis-2-butene to the trans-form at 2 ~ over a
transparent TS-1 film consisting of nanoparticles was demonstrated.[107] The TS-1
nanoparticles were also used for the preparation of fibers and porous monoliths, thus
providing a variety of formats for possible optical applications.[ 108,109]
Reviews covering this diverse area are available.[110,111] The former review covers the
photochemistry of nanostructured materials (including zeolites) for energy applications, the
latter the preparation and properties of chromophores in porous silica and minerals such as
zeolites.

3.2.4. Chemical sensors based on zeolite films

Chemical sensors are small devices for the detection and quantification of gaseous or
solvated species. This is an active research area based on the need to obtain increasing
amounts of data in chemical and food process streams as well as environmental monitoring.
Most sensors consist of an appropriate transduction principle such as the quartz-crystal-
microbalance (QCM) and a chemically sensitive layer that imparts the desired chemical
response behaviour. Most often a chemically selective response is desirable. Zeolite
molecular sieves offer size- and shape-selective adsorption behaviour that can be combined
with appropriate transduction concepts in order to construct chemically selective sensor
devices.

Acoustic devices
Acoustic wave devices such as the quartz-crystal-microbalance or surface-acoustic wave
devices have been combined with thin zeolite layers in order to impart the molecular sieving
capabilities onto the sensor device. The formation of acoustically coupled zeolite layers was
achieved according to different methods including dip-coating from a zeolite-binder
suspension, spin-coating from such a suspension, growth of a crystal layer, or attachment of
nanoscale zeolite crystals via electrostatic or covalent binding methods. Over the years it has
been demonstrated that different types of chemical selectivity in the sorption behaviour of
zeolites could be transferred to the acoustic wave device; this includes size- and shape
selectivity as well as hydrophilic-hydrophobic interactions. Typically, differences in uptake
between molecules entering the zeolite pores and those adsorbing only on the external surface
can amount to a factor of 100.[ 112] Thin layers of colloidal silicalite- 1 were electrostatically
pre-assembled on the gold electrode of a QCM, followed by hydrothermal growth of a dense
film of the zeolite.[113] This sensor system was highly sensitive for the detection of
hydrocarbon vapors.
A recent example shows the high sensitivity of LTA-type zeolite films on QCMs towards
low levels of humidity.[ 114] The films were obtained using secondary growth on a precursor
 281

seed layer consisting of zeolite seeds with a mean size of 40 nm that were adsorbed on silane-
modified sensor surfaces. The seed layers were subjected to hydrothermal treatment, thus
resulting in LTA-films with thicknesses of ca. 60-1000 nm. The thicker films showed, not
surprisingly, slower equilibration rates than the thinner films. However, reversible water
vapour sorption isotherms could be measured at room temperature in these thin films.
Zeolite Beta (BEA) films of 250 nm thickness were synthesized on the gold electrodes of
QCM-devices according to a similar approach and their sorption behaviour towards different
vapors was compared with that of zeolite LTA.[115] Due to the larger pore size of the BEA-
type films, the latter could adsorb larger organic molecules such as pentane, hexane and
cyclohexane, while the LTA-type films showed a selective response to water vapour only.
Further examples of acoustic sensors modified with zeolites include a QCM sensor with
silver-exchanged ZSM-5 that responds selectively to acetone (in diabetic's breath) in the
ppm-range,[ 116] principal component analysis of multiple QCM-sensor responses (with LTA,
MFI, SOD) for the detection of NO/SO2 mixtures,[117] MFI-zeolite-coated microcantilevers
with ppm-sensitivity for Freon detection [118,119] and other zeolite-coated cantilevers for
humidity sensing.[ 120]

Electrochemical and electronic devices

In contrast to equilibrium-based sensing such as described above, it is also possible to
use the zeolite film as a membrane controlling molecular access to an appropriate
transduction mechanism. In this case, Pd-doped semiconductor gas sensors were used as a
fairly non-selective sensor platform. After coating these sensors with a thin film of MFI-type
or LTA-type zeolites, they were examined with respect to gas phase sensing of different
analytes such as methane, propane and ethanol, at different humidity levels (Fig. 14).[121]
The response of a zeolite-coated sensor towards the paraffins was strongly reduced compared
to the non-coated sensor device, thus resulting in an increase of the sensor selectivity towards
ethanol.
MFI

organophilic/hydrophilic ~" 10e ~ ~'~

~ / , zeolitelayer o lOS ~
"~" " ~ ~ ~ ~ ' ~ S

[~ I [ Pd-dopedSnO2 ~
A1203subs~a~
I I 3 CH 25OOI~m EtOH 50~m
10 9 CH E~m
f ~ ~ heater
i ii
[nvM] resistancemeasurement I 100" 150 200' 2,50 "3Cl0"350- 41~ "450
(a) Time (min)

Fig. 14. Zeolite-modified Pd-doped SnO2 sensor design (left; DVM: digital voltmeter). The plots on
the fight display the sensor resistance as a function of the type and concentration of the organic vapour
(methane or ethanol). The measurements were done at 350 ~ with 0% relative humidity in the feed.
The data for the unmodified (reference) sensor and the sensors modified with layers of silicalite-1 and
zeolite A are shown. [ 121 ]

Another type of zeolite-filter was employed for the detection of hydrocarbons; in this
case a Pt-doped zeolite filter changes the selectivity of a titania conductivity sensor towards
282

propane in the presence of CO, presumably due to the resulting water of combustion.[122]
Related concepts were used for the detection of NO• 123,124]
Humidity sensors are often based on conductivity changes of hydrophilic substances, as
in the case of LiC1. This salt can be included into zeolites such as Y, and at suitable loading
levels a humidity-sensitive composite is obtained that is stable towards high humidity and
high temperatures and less susceptible to external contamination than bulk LiCI.[ 125]
The nature and mobility of ions and solvent in zeolite cages will affect the ac-impedance
of the material. This effect can be utilized for zeolite-based sensor concepts where a zeolite
film is coated on interdigitated electrodes. For example, it was shown that the impedance of a
film of proton-conducting H-ZSM-5 is influenced by the presence of ammonia (Figs. 15,
16).[126,127] The ammonia is protonated in the zeolite, thus producing much larger
ammonium ions with different mobilities in the zeolite that can be detected by impedance
spectroscopy. The detection of ammonia is of interest for automotive applications where the
selective catalytic reduction of NO• by ammonia is envisioned.

ammonia
zeolile film_
interd~gital ~ ~
capac~or~~-m-.~i-- i-~i -i i-I~._I
substrate - - I
heater ~---'O~L=~';,5~ z S ~ - Y - J ~
~ - substrate ~ cover J
(a) top side bottom side (b) cross section

Fig. 15. Schematic presentation of the sensor; (a) measuring electrode design coated with zeolite film
(top) and heater electrodes (bottom), (b) cross section. The resistance of the Pt heater is also used as
temperature sensor. [ 1271

45 -0 ppm- Oppm
!~-_~ 5 ppm
...._N10 pprn
40'
-'~20 ppm

35' 40 ppm
\
-~60 p~m
30- '

25 100 o o m

2O
0 200 400 600 800 1 0 0 0 1 2 0 0 1 4 0 0 1600
time [sec]

Fig. 16. Resistance changes of a zeolite-coated (H-ZSM-5) sensor exposed to different ammonia
concentrations. The resistance was derived from an RC equivalent circuit at 1 MHz measurement
frequency. [ 127]
 283

Optical sensor concepts

Optical responses of molecules or materials can offer several advantages in sensor
design: The response is often very fast, allowing for rapid response if needed, the response
can be transferred through space, across optical windows or fibers thus protecting the
analytical system or the measurement device, and, depending on the transitions involved, the
analyte may have highly structured spectroscopic features that may help to identify or
quantify it. A few recent examples will serve to illustrate these points.
The redox behaviour of highly dispersed mononuclear and clustered Ti-, Sn- and V-oxide
species in the pores of zeolites and mesoporous hosts was investigated as a means for oxygen
detection.[128,129] The authors found that the reversible optical changes of these materials
could be correlated to the number of oxygen vacancies in the particles, and that these changes
can be used for the design of an oxygen sensor.
Another approach is to encapsulate photoactive molecules in the cages of zeolites. The
complex tris(bipyridyl)ruthenium(II), Ru(bpy)3] 2+, was entrapped in highly siliceous zeolite Y
obtained by a dealumination reaction with silicon tetrachloride.[130] This was achieved by
adsorption of neutral Ru(bpy)Cl3 as a starting material. The oxygen sensing mechanism of
Ru(bpy)3] 2+ is based on emission quenching by dissolved oxygen. It was found that the
dealumination leads to a hydrophobic environment that favors oxygen diffusion from the
water into the zeolite. A thin film format where the zeolites are included in a siloxane layer
was also investigated.
Aromatic molecules such as naphthalene will emit phosphorescence when adsorbed in
zeolites exchanged with heavy ions such as thallium. This was exploited in a convenient,
zeolite T1Y-coated optical fiber format in order to detect naphthalene.[ 131 ]
Solvatochromic dyes offer the possibility to detect changes in the polarity/dielectric
constant of a solvent, resulting in a significant spectral change. If such a dye is included in the
cages of a zeolite, the solvent loading in the nanoscale cages in combination with the
molecular sieving behaviour of the zeolite will control the spectral signature of the dye, thus
acting as a sensor (Fig. 17).[132,133] This concept was realized with a number of
solvatochromic dyes such as nile red in dealuminated zeolites that showed fast and reversible
changes in absorption and fluorescence upon exposure to a variety of different molecules.

Fig. 17. Encapsulation of the dye nile red in siliceous zeolite Y in a multi-step synthesis. [132]

If a redox reaction causes a reversible optical change, this reaction could be used to
detect the concentration of the oxidant. This approach was incorporated into an elegant sensor
284

design for oxygen-detection at high temperatures.[ 134] The Cu(I) ions in the zeolite Cu-ZSM-
5 show a strong fluorescence at 550 nm, while reversible oxidation with oxygen produces
Cu(II) ions that do not emit in this region. This zeolite was embedded into a thin sol-gel
derived silica film on the tip of an optical fiber used for both excitation and detection of the
emission. This sensor was shown to detect oxygen at the level of a few hundred to a few
thousand ppm at 425 ~ with a fast response time of a few seconds and good reversibility.

Other concepts - microcalorimetry

Finally, we mention a novel transduction concept based on the heat evolved from a
reaction such as combustion. Microcalorimetric devices can now be made using lithographic
techniques. One of the two sensitive areas of such a device (were evolved heat can be
measured) was coated with a thin film of CoAIPO4-5, the other was kept open as a
reference.[ 135] The additional benefit of a zeolite with catalytic activity for such a device is
the molecular sieving effect that can be combined in the response of the sensor (a molecule
too big to enter the catalytically active interior of the zeolite should only show a weak
response). The change in temperature was measured with a meandering Pt-wire resistor. This
device was examined in the detection of CO and cyclohexane, and sensitivity and selectivity
in the low ppm-range was observed.

4. C O N C L U S I O N S

The well-defined nanoscale pore systems featured by zeolites are the basis for several
established types of applications such as heterogeneous catalysis, ion-exchange and gas
separation by selective adsorption. In the more recent past, however, researchers have also
explored opportunities in additional areas. This review has explored recent developments in
advanced applications of crystalline molecular sieves. It is apparent that the zeolite pore
systems with their extremely well-defined crystalline cages and channels, their ion-exchange
capability, and their tunable properties with respect to acid/base behaviour,
hydrophilicity/hydrophobicity can offer a platform for many novel functional concepts. In
addition, the growing ability to control the size and morphology of either zeolite single
crystals or zeolite intergrowths has opened up entirely new applications such as zeolite
membrane separations, chemical sensors or spatial confinement.

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