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Introduction
1.1 General introduction
Porous materials have been widely used as catalysts, adsorbents, molecular sieves,
ion exchangers and chromatographic agents in fine chemicals industry because of their
particular properties such as uniform pore size, large surface area and flexible
frameworks. Following the definition accepted by the IUPAC [1], porous materials can
be grouped into three classes based on their pore diameter (): microporous, < 2.0 nm;
mesoporous, 2.0 < < 50 nm; and macroporous, > 50 nm (Fig. 1-1). Among the
porous solids, microporous zeolites and mesoporous molecular sieves are mostly used as
acid catalysts, especially in the petrochemical industry. They possess several catalytically
desirable properties including high surface area, adjustable pore size, acidity and high
thermal stability [2-4].
Zeolites are crystalline porous solids containing pores and cavities of molecular
dimensions. Their structures reveal regular arrays of channels and cavities in the
molecular size range of 0.3 to 1.5 nm. In their acid form, zeolites are probably the most
important heterogeneous acid catalysts used in industry and are particularly used in the
fields of oil refining and petrochemistry as fluid cracking catalysts. Their key properties
are size and shape selectivity, together with the potential for strong acidity [5]. Although
the micropores of zeolite have been well described as having excellent potential for
chemical functions, diffusion in the micropores often interferes in chemical process [6].
This limits the application of these pore systems to reactant molecules having kinetic
diameters below 10 .
Microporous
Domain
Mesoporous
Domain
Macroporous
Domain
Porous Glasses
Porous Gels
M41S
Zeolites and
related materials
0,5
5
10
Pore Diameter (nm)
50
100
Fig. 1-1 Examples of micro-, meso-, and macroporous materials, showing pore size
domains and typical pore size distributions [1].
However, due to the amorphous nature of the pore walls, mesoporous materials generally
exhibit weaker acidity and poorer hydrothermal stability than conventional zeolites.
Therefore, a lot of efforts have been made to improve properties of mesoporous materials.
Among them, the synthesis of composite materials with combined micro- and
mesoporousity has become the challenging target. This kind of material is expected to
offer many significant advantages over single micro- or mesoporous molecular sieves
including improved diffusion rate, high acidity and hydrothermal stability.
8-Ring, zeolite A
12-Ring, zeolite Y
Zeolites have been the most important solid acid catalysts in the past few decades. A
landmark was the introduction of synthetic faujasites (zeolites X and Y) on an industrial
scale in fluid catalytic cracking (FCC) of petroleum to produce the majority of the
worlds gasoline - one of the most important chemical processes worldwide. ZSM-5 is
another example being of utmost importance in heterogeneous catalysis. It is used
Fig. 1-3 Structure of zeolite Y (FAU) [9]. 12-ring viewed along [111]; supercages : 13
.
Fig. 1-4 Projections along principal crystallographic directions of zeolite beta structures:
polymorph A (left) and Polymorph B. The unit cell outlines are indicated by the dashed
lines [10].
The structure of zeolite beta was only recently determined because the structure is
very complex. Zeolite beta consists of an intergrowth of two distinct but closely related
structures termed Polymorphs A and B (Fig. 1-4) which are normally found in a 60:40
ratio, respectively. Both polymorphs have three-dimensional 12-ring pore systems. The
intergrowth of the polymorphs does not significantly affect the pores in two of the
dimensions, where two mutually perpendicular straight channels with a cross section of
7.6 x 6.4 run in the a- and b-directions. However, the pore becomes tortuous in the
direction of the faulting, where a sinusoidal channel of 5.5 x 5.5 runs parallel to the cdirection (Fig. 1-5). The two polymorphs are depicted in references [9-13]. It has been
proposed that a third polymorph C should also exist which has a 3-dimensional pore
topology with all 12-membered-ring channels being linear. Indeed, pure polymorph C of
zeolite beta was synthesized by using framework isomorphous substitution (Si replaced
partially by Ge) as a structure-directing mechanism [14].
(a)
(b)
Fig. 1-5 Structure of zeolite beta. (a) 12-ring viewed along [100] and (b) 12-ring viewed
along [001] [9].
(i) nucleation rates are reduced so that larger crystals are formed and (ii) the acid or
neutral pH regime facilitates the structural incorporation of those heteroatoms where the
precursor species would be precipitated at higher pH [18]. In recent years, this approach
comes to great prominence, particularly in the synthesis of large crystals, novel structures
and hetero-substituted materials. For example, incorporation of Ti into the framework of
Al-free zeolite beta in F- medium was achieved by Corma et al. [19]. It was found that
upon contact with ambient humidity, there is no hydrolysis of Si-O-Ti bonds in Ti-Beta
zeolites prepared by the fluoride route, while it is probably a major feature of those
synthesized in OH- medium. The more hydrophobic character of Ti-beta-F (synthesized
in the fluoride media) gives it attractive properties in oxidation reactions. Furthermore,
Al-free Sn-beta zeolite was successfully synthesized in fluoride medium [20] and it is
shown to be a very efficient catalyst for Baeyer-Villiger oxidation. Recently, Al-free Zrbeta zeolite with Si/Zr up to 75 was synthesized in fluoride medium by our group [21].
The incorporation of zirconium into zeolite beta induced the formation of increased
amounts of polymorph B. Moreover, Zr-beta was found to be excellent catalyst in the
MPV reduction of alkyl- and aryl-substituted cyclohexanones, with high selectivity to the
corresponding alcohols.
10
H
O
Si
O
O
O O
Si
O
O O
Al
Si
O O
O
O O
Si
O
O
Fig. 1-6 Brnsted acid site formation due to Si/Al substitution in a zeolite framework
Brnsted acid sites are formed by the bridging hydroxyl protons which compensate
the excess negative charges generated by isomorphous substitution of silicon with
trivalent metal cations, Al3+ for instance, into the framework. In zeolites, the bridging
hydroxyl groups are attached to framework oxygen linking tetrahedral Si and Al atoms
(Fig. 1-6). Obviously, the number of protonic sites in a zeolite is related to the number of
framework aluminum atoms. While aluminum incorporation in the framework results in
Brnsted acidity, extra framework aluminum (or more accurately aluminum
oxyhydroxides) in the pore system results in Lewis acidity [22]. Extra framework
aluminum species created by mild steaming or calcination of hydrated zeolites were
shown to increase the catalytic activity of zeolites. This increase in activity was attributed
to the creation of sites exhibiting enhanced acidity through interaction of bridging
hydroxyl groups (Brnsted acid sites) and neighboring small extra framework aluminum
species (Lewis acid sites) [23]. However, the exact nature is still a matter of debate.
11
12
13
14
16
Fig. 1-8 Transition states for the formation of cis-4-tert-butyl-cyclohexanol (left) and
trans-4-tert-butyl-cyclohexanol (right) in the proposed reaction mechanism over zeolite
beta. Illustration from Ref. [32].
17
18
two parameters: the balance between hydrogenating and acid functions [41] and the
zeolite pore structure [42].
Apart from its functions as a metal support and an acidic catalyst, the zeolite
component may also induce shape selectivity, i.e., employing a zeolite as carrier for a
metal enables the shape-selective properties of the microporous structure to be conferred
on the catalytic reactions [43]. Dessau [44] studied the competitive hydrogenation of
branched 4,4-dimethyl-1-hexene and linear 1-hexene over Pt/Cs-ZSM-5. He showed that
over platinum clusters located inside the pores of zeolite ZSM-5, the linear olefins are
preferentially reduced over the branched olefins. However, when the metal was located in
the external surface, no shape selectivity was observed. Therefore, this finding was also
exploited as a method to assess the location of platinum in Pt/Cs-ZSM-5. Moreover, it
was found that the shape selectivity could be obtained only by reduction of the catalyst in
the presence of olefins and hydrogen but not for catalysts reduced in pure hydrogen. This
was explained by metal migration from the interior of the zeolite to the external surface
during the reduction process in hydrogen while the olefins reacted with the platinum
hydride species, thus preventing their migration and agglomeration. Another example for
shape-selective, metal-catalyzed reaction is the selective oxidization of para-xylene in
the presence of the bulkier ortho-xylene over copper-loaded ZSM-5 [45]. Creyghton et al.
[46] reported that 1-decene reacted 18 times faster than trans-5-decene over Pt/Na-beta,
whereas the ratio was only about 2 for platinum on non-microporous supports. This
regioselectivity was attributed to the steric constraints imposed by the microporous
structure of the zeolite. Moreover, regioselectivity was only obtained when the nonselective, external-surface located platinum clusters were selectively poisoned with
19
layered
polysilicate
kaenemite
in
an
aqueous
solution
of
20
templating agents was first developed by a research group at Mobil Oil in 1992 [48]. This
led to a new family of mesoporous silica and aluminosilicate compounds (M41S). These
solid phases are characterized by ordered mesopores presenting narrow pore size
dispersions. The M41S family includes a bidimensional hexagonal phase (MCM-41, for
Mobil Composition of Matter), a cubic phase, MCM-48, and several lamellar phases.
MCM-41 is synthesized by using amphiphilic templating materials together with
inorganic precursors to self assemble into a hexagonal array of uniform pores. The most
outstanding feature in the preparation of MCM-41, in contrast to the traditional single
organic molecule or metal ion templating preparation, is that the templates used are
surfactants, having an alkyl chain length of greater than 10 carbon atoms. Therefore, the
mechanisms responsible for the formation of MCM-41 have attracted much attention.
Several models for the formation of MCM-41 have been proposed [49], e.g., liquid
crystal templating (LCT) approach [48]; transformation mechanism from lamellar to
hexagonal phase [50-53]; and silicate-template interaction hybrid polyelectrolyte model
[54]. All these models are based on one principle: surfactant molecules play a central role
in directing the formation of the inorganic mesostructure from soluble mineral species
[55].
In comparison to microporous zeolites, ordered mesoporous materials with large pore
dimensions overcome the pore size constraint and allow the diffusion of larger molecules.
Moreover, mesoporous molecular sieves present very high surface areas with very regular
pore size dimensions which make them good candidates as support for catalytically active
phases. The introduction of transition metals in the walls gives them catalytic redox
properties which are useful in selective oxidation reactions. However, it was immediately
21
recognized that mesostructured materials have relatively low acidity and poor stability, in
contrast to requirements of many catalytic applications. The instability of these structures
can be attributed in part to the thinness and incomplete crosslinking of the pore walls.
Recent effort has been focused on improving both the acidity and the hydrothermal
stability of mesoporous materials.
22
23
24
25
27
crystalline zeolite Y. Normally, a single 27Al NMR peak at a chemical shift near 55 ppm
is observed for conventional Al-MCM-41 [72]. The higher chemical shift of the
tetrahedral aluminum sites, together with the stronger acidity of Al-MSU-S for cumene
cracking, implies that zeolite-like connectivities were retained in the Al-MSU-S material.
Besides HY seeds, pentasil zeolite seeds, such as BEA and MFI type seeds have been
used to make micro/mesoporous materials [70, 73-74]. In comparison to the faujasitic
zeolite seeds, which are nucleated by sodium ions, pentasil zeolite seeds are nucleated by
specific tetraalkylammonium ions. Pinnavaia et al. [75] prepared hydrothermally stable
and strongly acidic MCM-41 analogs from zeolite ZSM-5 and Beta seeds, which are
nucleated by tetrapropylammonium and tetraethylammonium cations, respectively. They
proposed that the hydrothermal stability and catalytic activity of MSU-S (MFI) and
26
MSU-S (BEA) arise from the presence of zeolitic subunits of AlO4 and SiO4 tetrahedra in
the framework walls of the mesostructures. Evidence for the retention of a protozeolitic
connectivity of tetrahedra was provided by IR spectroscopy. Zhang et al. [74] also
reported a hydrothermally stable MCM-41 analog, MAS-5, which was assembled from
zeolite beta seeds. The workers claimed that MAS-5 showed stronger acidity than
conventional Al-MCM-41 for 1,3,5-triisopropylbenzene cracking and higher catalytic
activity than zeolite beta for the alkylation of 2-butene with isobutene. Although the
acidity of MAS-5 reported to be very similar to zeolite beta, the higher catalytic activity
for the alkylation was attributed to the easier diffusion of products in the mesoporous
channels of MAS-5 than in microporous zeolite beta. Xia and Mokaya [76, 77]
synthesized ZSM-5/MCM-48 using a simple two step crystallization process which
involved the assembly of precursor zeolite species, containing ZSM-5 units at various
stages of crystallization, into a mesostructured material. It was found that the acidity and
hydrothermal stability of the composite materials was strongly dependent on the extent of
zeolite phase, i.e., ZSM-5/MCM-48 ratio.
Usually,
the
production
of
these
micro/mesoporous
materials
use
27
28
(MFI) and faujasitic zeolite type Y (FAU) gel solutions [82]. With steam treatment, the
coated samples showed much more hydrothermal stability than the parent MCF sample.
This was attributed to the zeolite seeds coated on the mesopore surface, which create
valence bonds with the precursor and heal defect sites, reducing consequently the
concentration of silanol groups. Therefore, it was concluded that zeolite-coated MCF are
promising as new acid catalysts for the conversion of bulky molecules at high
temperature.
The use of protozeolitic nanoclusters for the preparation of improved mesostructures
is not limited to aluminosilicates. Metal-substituted seed compositions, such as those
used to nucleate TS-1, Ga-MFI, and AlPO, may be used as precursors for the preparation
of stable mesostructures [83].
30
31
32
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