AKTA KIMIA

Akta Kimindo Vol. 1 No. 1 Oktober 2005: 1 – 10 INDONESIA

Nanomaterials as catalysts in the production of fine chemicals*)

Halimaton Hamdan1)

Ibnu Sina Institute for Fundamental Science Studies

Universiti Teknologi Malaysia
Skudai, Johor, Malaysia

ABSTRACT
Zeolit and mesomorphous materials are porous materials with windows, channels and cavity
architectures of nanometer dimensions. Large pore zeolites, mesomorphous MCM-41, MCM-48 and silica
aerogels have been synthesized from rice husk. The growing interest in these novel systems is due to the
bulk behaviour of these nanostructured materials which can be designed and tailored by controlling their
cluster nanostructures which lead to greatly improved performance. Changes in the molecular properties of
materials at the nanoscale level greatly enhance their physical and chemical properties. The zeolite lattice
may also be used as a host for encapsulated complexes or metallic clusters allowing the control of
nuclearity of these active species. MCM-41, for examples and enzymatic species to from molecular wires,
zeozymes and hybrid catalyst.

ABSTRAK
Zeolit dan mesomorfosa adalah bahan berpori dengan arsitektur jendela, terowongan dan rongga
yang berdimensi nanometer. Zeolit berpori besar, mesomorfosa MCM-41, MCM-48 dan silika aerogel telah
disintesis dari sekam padi. Pertumbuhan yang menarik dari sintesis baru ini adalah struktur bahan yang
berukuran nano dapat didesain dan dibuat melalui pengontrolan kluster struktur nano yang memberikan
kinerja yang sangat luas. Perubahan dalam sifat molekuler bahan pada tingkat skala nano meningkatkan
sifat fisik dan sifat kimianya. Kisi-kisi zeolit dapat juga digunakan sebagai host (sarang) untuk
membungkus komplek atau kluster logam yang memungkinkan untuk mengontrol keterpusatan spesies
aktif ini, MCM-41 misalnya telah digunakan untuk sarang polimer, komplek logam dan spesies enzim untuk
membentuk kawat, zeoenzim dan katalis hibrida.

INTRODUCTION systems is due to the bulk behaviour of these

An exciting new scientific trend emerged
in the 80’s for exploring zeolites and
mesomorphous materials, as advanced solid-
state materials. Zeolites and mesomorphous
materials or commonly referred as molecular
sieves, are porous materials with nanometer
dimension (0.3–10 nm) windows, channels and
cavity architectures. They represent a ‘new
frontier’ of solid-state chemistry with great
opportunities for innovative research and
development.
The most recent efforts is to find several
novel applications which include molecular
electronics, “quantum” dots/chains, zeolite
electrodes, batteries, nonlinear optical materials,
enzyme mimics, chemical sensors, molecular
wires and nanodevices (Frost and Sulivan,
2001).
*) Makalah kunci yang disajikan pada
Nasional Kimia VII, di Surabaya 9 Agustus 2005
1) Corresponding author
The growing interest in these novel
nanostructured materials which can be designed
and tailored by controlling their cluster
nanostructures which lead to greatly improved
performance. In addition, the characteristics of
these nanomaterials could be purposely
engineered by the variation of the chemical
composition, structure and size distribution
(Frost and Sulivan, 2001; Barrer, 1982; Breck,
1974; Meier and Olson, 1987 ).
In tandem with numerous research
findings which are continuously being reported by
about 20000 zeolite scientists globally, we have
made some important discoveries that contribute
to the development in the science and
nanotechnology of zeolites and mesomorphous
materials. This paper presents a general review
of our contributions and recent advances in the
design and investigation of these fascinating
Seminar
family of nanostructured materials.

© Kimia ITS – HKI Jatim 1

 Hamdan - Nanomaterials as catalysts in the production of fine chemicals

ZEOLITES AND MESOMORPHOUS MATERIALS

Zeolites are crystalline, hydrated
aluminosilicates with open three-dimensional
framework structures (Barrer, 1982; Breck, 1974)
built of (SiO4)4– and (AlO4)5– tetrahedra linked by
sharing of an oxygen atom, to form regular
intracrystalline cavities and channels of molecular
dimensions. The first natural zeolite molecular
sieve, stilbite, was discovered by Cronstedt in zeolite A Zeolit Y
1756. He named it ‘zeolitos’ which means boiling
stone, because the mineral appeared to boil when
heated. Since then about 45 natural zeolites have
been identified.
In 1862, St. Claire Deville attempted,
unsuccessfully, to prepare a synthetic zeolite.
Barrer’s pioneering work in the 1940’s
demonstrated that a wide range of zeolites could
be synthesized from aluminosilicate gels (Frost
and Sulivan, 2001; Barrer, 1982). In 1956, Linde
A, the first commercial zeolite was synthesized by
Breck (Breck, 1974). In 1962 Mobil Oil introduced ZSM-5 zeolite beta
the use of synthetic zeolite X as a cracking
catalyst, followed by the synthesis of the high
silica zeolites beta and ZSM-5. Today at least 150
synthetic zeolites are known.
Mesoporous MCM-41 and aerogels are
nanostructured materials with great potential as
catalyst and nanocomposites. The interest in new
zeolite-like materials or mesomorphous materials
reflects the importance of improving the
performance of zeolites as molecular sieves or
catalysts. The major problem in the zeolite area is
an apparent restriction of pore size to less than
0.8 nm. There have been numerous attempts to ferrierite mordenite
incorporate the selectivity and resilience of zeolite
into a structure which has significantly larger pore Figure 1 : Framework topologies of various zeolites
size which is capable of processing large
hydrocarbon molecules. With mesoporous solids
for instance, shape selectivity whose effects on ii) Mesomorphous MCM-41
reactants, products and transition states are well In 1992, a new family of silicate
known in microporous systems may be extended mesoporous materials, designated as M41S, with
to larger molecules. exceptionally large uniform pore structures has
been synthesized. Among these materials, the so-
called MCM-41 family which shows a hexagonal
STRUCTURAL CHARACTERISTICS array of uniform mesopores in the range between
(i) Zeolites 1.6 nm and 10 nm as shown in Figure 2. The
The various types of zeolites are MCM-41 structures were found to be constructed
characterized by the distinct topology of their mainly from amorphous inorganic silica walls of
three-dimensional framework, the relative content 0.9 to 1.2 nm in thickness around surfactant
of silicon and aluminium, the ordering of the molecules. The calcined material have specific
silicon and aluminium atoms in the tetrahedral surface areas of about 700 m2 per gram. A so-
sites of the framework and the type and called liquid crystal templating mechanism in
distribution of cations. The framework topology which surfactant liquid crystal structures serve as
and morphology of zeolites contribute to the organic templates has been proposed to explain
remarkable physical and chemical properties of the formation of such large pore sizes in the
these microcrystals. Some of the framework mesoporous materials. Burning off of the organic
topologies found in zeolites are shown in Figure 1 material then leaves back the cylindrical pores.

2 © Kimia ITS – HKI Jatim

Akta Kimindo Vol. 1 No. 1 Oktober 2005: 1 – 10

being recognized by designers, engineers and

architects. Silica aerogel is a potential substitute
for silicon dioxide, the reigning dielectric. Silica
aerogel offers a better way to keep the
interconnecting wires from shorting across the
narrow dividing space between transistors which
avoid propagation delays and excessive crosstalk
and subsequently may double computer speeds.
Ultralow density (ULD) silica aerogels
have been taken on NASA space shuttle missions
Figure 2: Schematic representation of the to capture high velocity cosmic dust particles.
structure of a MCM-41 phase with an Furthermore, aerogels are also being used by
interpore distance of ≈ 3.5 nm, NASA to insulate the rover vehicle for the Mars
amorphous wall structure and hexagonal Pathfinder project in 1997.
pores. Maerogel; a silica aerogel which is
directly prepared from rice husk (Figure 4) is a
(iii) Silica Aerogel nanomaterial of a highly divided state and exhibits
In a recent issue of Science, aerogel was unconventional properties which offers more cost
rated among the top ten scientific and effective methods of production and application.
technological developments (Nur, et al., 2005). Maerogel is more superior in quality than the
Aerogels are advanced materials yet are literally current commercial TEOS aerogel. Being an inert,
next to nothing. They consists of more than 96% non-toxic and environmentally friendly amorphous
air and the remaining four percent is a matrix of material, Maerogel possesses established
silica (Figure 3). Aerogels are unique materials physico-chemical properties al listed in Table 1
with pores and properties which are smaller than which can be modified for specific applications.
the wavelength of light. Aerogel is the lightest
solid material known; only three times the density
of air and has tremendous insulating capability.
Aerogel is a good insulator because of its
large internal surface area. It disperses heat
throughout its complex structure and aerogel
makes possible development of extremely
interesting applications in vacuum and heat
insulation of hot water tanks and boiler,
refrigerators and industrial ovens. A double pane
window filled with a one inch layer of aerogel
provides the same insulating value as 15
standard thermopanes. It is just a question of
time as to when technology and markets offer the
benefits of “translucent” building components
that feature full control of heat performance. A
promising material for translucent roofing is silica
aerogel.

OH

HO O Si O OH
Si Si
O O O
O Si O
Si
O O
O
Si Si
HO O OH
O Si

OH

Figure 3: Silica matrix in aerogel

Figure 4: SEM micrograph and photograph of Maerogel

Aerogels are inert, non-toxic, environmentally
friendly insulation materials and, its superior
performance over other foam materials is finally

© Kimia ITS – HKI Jatim 3

 Hamdan - Nanomaterials as catalysts in the production of fine chemicals

Table 1: Physical Properties of Maerogel conversion and selectivity of 2-phenyl-1-propanol.

(Mohamed, 2005)
Property Maerogel
Apparent density 0.03 g/cm3
Internal Surface Area 800-900 m2/g
Mean Pore Diameter 20.8 nm
Thermal Tolerance to 500 C, mp > 1200 C
Thermal Conductivity 0.099 Wm-1 K-1

NEW DIRECTIONS
Nanostructured Materials
Large pored zeolites, mesomorphous
MCM-41 and silica aerogels are naturally

Rel Intensity
nanomaterials due to the existence of pores and
crystalline network of nano dimension. Changes in
the molecular properties of materials at the Zeolite A
nanoscale greatly enhance their physical and
chemical properties. Due to its stable and flexible
- 56
framework of variable sizes, the zeolite lattice may Dir-Al-MCM-
also be used as a host for encapsulated
complexes or metallic clusters allowing the control
of nuclearity of these active species and the steric Dir-Al-MCM-
contraints imposed on the reactants. MCM-41 and
VPI-5, for example, have been used to host Dir-Al-MCM-
polymer, metal complexes and enzymetic species
to form molecular wires and zeozymes.
(i) Al-MCM-41 catalysts were prepared with Sec-Al-MCM-41
various SiO2:Al2O3 ratios via direct and
secondary syntheses using sodium aluminate as Dir-Al-MCM-
the aluminium source. Structural studies by 27Al
and 29Si MAS NMR spectroscopy indicated that Al
are in the tetrahedral form and located in the - - 0 ppm
framework. The presence of distorted framework Al(H2O)63+
aluminium was also observed, more significantly Figure 5 27Al MAS NMR spectra of Zeolite A and Al-
in the secondary aluminated samples. Maximum MCM-41 samples with various SiO2:Al2O3
amount of Al was incorporated by direct synthesis ratios
with SiO2:Al2O3 ratio of 10 and a calculated Si/Al
Am ount of d esired product (m m ol)

ratio of 15.2. Acidity studies using Pyridine 3

Desorption Measurement and Temperature 2.5
Programmed Desorption of Ammonia 2
(TPD-NH3) show that the acidity of Al-MCM-41
1.5
increases with increase in Al incorporation into the
MCM-41 framework. The potential of H-Al-MCM- 1

41; as a heterogeneous catalyst was studied in 0.5

the hydroxyalkylation of benzene with propylene 0
oxide as a model reaction. Gas chromatography without 10 20 40 80 sec-
analysis indicates that H-Al-MCM-41 with catalyst AlMCM-
SiO2:Al2O3 ratio of 10 demonstrates the highest Catalyst (SiO2:Al2O3) 41
catalytic activity with a conversion of benzene and
selectivity of 92.3% and 87.5% respectively. The
formation of 2-phenyl-1-propanol was optimized at
a temperature of 393 K after 24 hours with Figure 6 Amount of 2-phenyl-1-propanol (desired
propylene oxide to benzene mol ratio of 0.5 using product) (mmol) with various SiO2:Al2O3 ratio at
nitrobenzene as the solvent. The results indicate constant parameter (Temperature: 363 K; Reactant
that instead of aluminium content, solvent and Mole Ratio: 0.5; Time: 24 hours; Solvent:
reactant mole ratio also play a role to give high Nitrobenzene)

4 © Kimia ITS – HKI Jatim

Akta Kimindo Vol. 1 No. 1 Oktober 2005: 1 – 10
(ii) The development of heterogeneous
oxidation catalysts which contain metal
complexed Schiff bases such as phthalocyanine,
porphyrin and salen that mimic catalytic activity of
metaloenzyme is of interest. Encapsulated metal
complex, as the guest molecule, into molecular
sieves with suitable pore sizes such as zeolite Y,
VPI-5 and MCM-41 as the host, via covalent or
ionic bonding is expected to be as active as those
present in enzyme, structurally and thermally
more stable, remain unchanged during reactions
and give higher conversions (Figure 7).
Figure 7: Metal complex encapsulated molecular sieves
In situ synthesis of Fe(III)-salen and Cu(II)-
salen complexes, Mn(III) complexes based on
diimine and aroylhydrazone ligands in the cavities
of Al-MCM-41, by the flexible ligand method were
attempted with success in our laboratory. The
catalytic activity of the Fe(III)-salen-Al-MCM-41
complex was studied in the oxidative
polymerisation of bisphenol-A using aqueous 30%
H2O2 at room temperature.
Cun+ salen
Cu2+ T=140oC,
T=80oC, Nitrogen
air gas
ZEOZIM Cu-salen-Al-MCM-41
© Kimia ITS – HKI Jatim
Table 2. Catalytic tests on polymerization of
bisphenol-Aa
Quantity of Percentage
Catalyst Polybisphenol- of reacted
A (g) bisphenol-A
Fe(III)-salen
0.22 19.3
(FS)
FSAM-40 0.76 66.7
FSAM-60 0.71 62.3
FSAM-120 0.38 33.3
aAllreactions were carried out at room temperature for
3 h: 100 mg catalyst; 5 mmol bisphenol-A; 3.4 mL 30%
H2O2; 10 mL dioxane
X-Ray diffractograms of all samples
demonstrate that the structure of Al-MCM-41 are
still intact after modification process with slightly
decrease in crystallinity. The immobilization of
salen ligand increases the pore diameter and unit
cell parameter of support due to the steric effect.
From DRUV-Vis spectra, it is observed that the
geometry of Table 2. Catalytic tests on
polymerization of bisphenol-Aa
Mn(Salen) and Co(Salen) complexes are
distorted upon encapsulation which can be
evaluated from the splitting of d-d electronic
transition. The main product of benzyl alcohol
oxidation is benzaldehyde and this molecule can
undergo further oxidation to produce benzoic acid.
It is observed that the encapsulated Fe(Salen)
catalyst shows the best substrate conversion
followed by Co(Salen) and Mn(Salen).
(iii) Dibenzoylation of benzoyl chloride in the
presence of mesoporous H-Al-MCM-41 forms the
biphenyl 4,4’-dibenzoylbiphenyl (DB) with 100%
selectivity. Catalytic results indicate that samples
with higher Si/Al ratios produced higher yields of
4,4′-dibenzoylbiphenyl. Sample with the highest
Si/Al ratio produced 0.45 µmol 4,4′-dibenzoyl
biphenyl; the highest yield, after 3 hours of
reaction. The catalytic test results indicate that
the product yield is influenced and determined by
the presence of both Lewis and Brønsted acid
sites. (Figure 8)
5
 Hamdan - Nanomaterials as catalysts in the production of fine chemicals

nor addition of co-solvent, were placed at the

phase boundary in order to catalyze the reaction.
It is of interest to enhance the activity of PBC
system The activity enhancement of the PBC
system by fluorination was explored. Hydrogen
peroxide was chosen as the oxidizing agent
because it produces only water as the by-product.
In addition, it is cheaper and more accessible
than other oxidant.
NaY zeolite was used as the host material
for the phase-boundary catalyst. Titanium
tetraisopropoxide was impregnated from
cyclohexanol solution into NaY zeolite powder to
give Ti-NaY. After that, the mixture was suspended
in toluene solution containing
octadecyltrichlorosilane (OTS). The fluorination
was carried out in 1M ammonium
hexafluorosilicate solution [(NH4)2SiF6] to give
F-PB-NaY. In the epoxidation reaction, 1-octene (4
ml), 30% aqueous H2O2 (1 ml) and the catalyst
powder (50 mg) were placed in a glass tube. The
reaction was performed with or without stirring for
24 hours at ambient temperature.
Figure 8: 27Al MAS NMR spectra of (a) SO4-AlMCM-
41, (b) H-AlMCM-41, (c) cal-AlMCM-41 and (d)
SO4-AlMCM-41 after treatment with 1.0 M
methanolic HCl solution.

(iv) Sulphated AlMCM-41 (SO4-AlMCM-41)

mesoporous molecular sieves with SiO2/Al2O3
ratio=15 was prepared via impregnation of (a)
sulphuric acid on the surface of H-AlMCM-41.
Absorbance / a.u.

Results of this work (Table 3) demonstrate that

SO4-AlMCM-41 is a solid Brönsted acid and active
towards benzoylation and dibenzoylation of
biphenyl. The production of 4, 4’-DBBP is affected
by the amount of acid site, amount of biphenyl
and 4-PBP. The conversion of biphenyl over H-
AlMCM-41 and sulphuric acid, sulphuric acid, SO4-
AlMCM-41 and sulphated amorphous silica are (b)
83.7, 90.6, 75.0, 94.2 and 22.3%, respectively.
The selectivity towards 4-PBP over H-AlMCM-41,
the mixture of H-AlMCM-41 and sulphuric acid,
sulphuric acid, SO4-AlMCM-41 and sulphated 1640 1600 1560 1520 1480 1440 1400
amorphous silica (SO4-silica) are 83.7, 11.1, 19.3, -1
Wavenumber / cm
83.2 and 22.1%, respectively. The SO4-AlMCM-41
which contains octahedral aluminium related to
Figure 9: The pyridine-FTIR spectra of (a) SO4-
the presence of Bronsted acid (Figure 8 and 9)
AlMCM-41 and (b) H-AlMCM-41 at 250 oC.
was found to be active towards dibenzoylation of
biphenyl reaction, giving 11.0% of 4, 4’-DBBP
whereas sulphuric acid and H-AlMCM-41 catalyst
which contains both Lewis and Bronsted acid sites
only produced 4.1% of 4, 4’-DBBP

(v) Recently, a novel concept of “phase-

boundary catalysis” (PBC) in the catalysis of
immiscible liquid-liquid reaction system was
proposed. In the PBC system, the bifunctional
particles containing both the hydrophilic and
hydrophobic regions, which require neither stirring

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Akta Kimindo Vol. 1 No. 1 Oktober 2005: 1 – 10

Table 3: Benzoylation and dibenzoylation of biphenyl with benzoyl chloride over various types of catalysts at
180oC for 24 h.

Catalyst(s) Conversion of BP Selectivity towards 4- Selectivity Selectivity

(%) PBP (%) towards 4, 4’- towards others
DBBP (%) (%)

H2SO4 a 75.0 35.3 0.0 39.7

H-AlMCM-41 83.7 83.7 0.0 0.0

H2SO4 + H-AlMCM-41 90.6 13.0 1.65 76.0

SO4-AlMCM-41 94.2 83.2 11.0 0.0

SO4-Silica 22.3 22.1 0.0 0.2

a Homogeneous catalyst.

Activity comparison in Table 4 between Consequently, titanium as the active site for
phase-boundary catalysts (PB- and F-PB-) and epoxidation reaction is further activated by
hydrophilic catalysts (Ti- and F-Ti-) of all catalysts fluorination. Amphiphilic fluorinated Ti-NaY
(Figure 10) on the epoxidation of 1-octene to give catalysts showed a remarkable activity
1,2-epoxyoctane indicated that the amphiphilic enhancement as observed in the F-PB-NaY
catalysts are more feasible for epoxidation. When catalyst which gives the highest TON/BET
the amphiphilic particles are placed at the phase
vi) Titanium containing silica aerogel was
boundary with the hydrophobic side facing the 1-
prepared by the sol-gel method. The tetrahedral
octene phase and the hydrophilic side facing the
titanium is present in low titanium loading, TSA1
H2O2 phase, titanium active sites on the catalysts
(Si:Ti = 200) is responsible in the catalysis of
are in contact with both the octene substrate and
cyclohexene to 1,2-cyclohexanediol as a major
H2O2. This resulted in a continuous supply of H2O2
product in the presence of hydrogen peroxide.
and alkene substrate to the active sites on the
Higher titanium loaded silica aerogel, (TSA2 (Si: Ti
particles. Fluorine is the most electronegative
=33) absorbs at 250 nm in UV DRS, suggesting
element. Being electron deficient, it has a high
the presence of [Ti(SiO)3O-] species. Selectivity of
tendency and affinity to attract electrons from its
TSA2 is tuneable by changing the loading of the
nearby element. Based on this nature, fluorine
catalyst in the reaction mixture. TSA1 catalysed
which was introduced to the catalyst by
cyclohexene to produce 1,2-cyclohexanediol at
fluorination would draw the electron from titanium
low loading and 2-cyclohexene-1-one when the
active sites towards the fluorine sites (Ti4+→F-).
loading was doubled.(Figure11)

Table 4: Epoxidation of 1-octene by various modified Ti-NaY catalysts

TON/BET
Catalyst Epoxide (μmol) BET (m2/g) TON for Ti ( x 10-3)

None 0.0 - - -

Ti-NaY 74.9 718.46 3.0 4.18

PB-NaY 94.1 118.04 3.8 32.19

F-Ti-NaY 111.2 22.37 4.4 196.69

F-PB--NaY 172.5 14.20 6.9 485.92

All reactions were carried out at room temperature for 24 hours with 1-octene (4 ml), 30% H2O2 (1 ml) and catalyst (50
mg) with vigorous stirring. The concentration of Ti and OTS = 500 μmol g-1.

© Kimia ITS – HKI Jatim 7

 Hamdan - Nanomaterials as catalysts in the production of fine chemicals

Figure 10: Photographs of modified Ti-NaY catalysts: Ti-NaY, OTS-Ti-NaY, F-Ti-NaY, OTS-F-Ti-NaY and TMS-F-Ti- NaY (from
left tto right).

31.3mg importance as sorbents, molecular sieves and

70
TSA2 catalysts. Zeolites are potentially very active
60 62.5mg catalysts due to the topology of the framework,
50 TSA2 shape and size of the pores which can be
125mg
modified to accommodate sorbates and impose
40 TSA2
shape selective contraints on the products of the
30 reaction. It is apparent that more applications of
20 these remarkable zeolite systems will be realised
as our knowledge of the chemistry and structure
10
of the framework continues to grow.
0 Improvements in the technologies for the
Alkene Glycol Keton Others synthesis of zeolites and development of zeolites
with larger pore sizes hold great promise in
70 better use of the depleting petroleum resources.
31.3mg
60
TSA1 Industrial application of aerogel-based
62.5mg catalyst or catalyst supports have so far been
TSA1
50 limited due to the rather expensive method of
preparation and difficulties in reactors operation.
40
Production of silica aerogel from rice husk does
30 not only reduce the cost but at the same time
minimise prolonged environmental problem. The
20 future beneficial use of aerogels in catalysis
mainly requires tailoring and design of the
10
surface structure and overcoming the technical
0 limitations.
Alkene Glycol Keton Others
REFERENCES
Figure 11: The component percent in the reaction
mixture after reaction using (a) TSA1 and (b) TSA2 as Barrer, R. M. 1982. Hydrothermal Chemistry of
catalyst Zeolites. Academic Press, London
Breck, D. W. 1974. Zeolite Molecular Sieves:
Structure, Chemistry and Use. John Wiley
CONCLUDING REMARKS AND FUTURE and Sons, London.
OUTLOOK
Several features of the structural
chemistry of zeolites are related to their

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Akta Kimindo Vol. 1 No. 1 Oktober 2005: 1 – 10
Chai, Lee Soon and Hamdan, H., 2004, Proc. of
the 2nd Annual Fundamental Science
Seminar AFSS 2004, ISBN-983-9805-54-
1, 2005, 138-140.
Frost and Sullivan, 2001. Zeolites Industry
Trends and Worldwide Markets in 2010.
Technical Insights, New York.
Hamdan, H. 2003. Design and Molecular
Engineering fo Nanostructured Zeolites
and Mesomorphous Materials
Professorial Inaugural Lecture, UTM, Siri 7,
Penerbit UTM.
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Hamdan, H., Navijanti, V., Nur, H., and Mohd
Nazlan Mohd Muhid, J. of Solid State
Sciences, 2005 Vol 7, Issue 2, 239-244.
Halimaton Hamdan, Vivin Navijanti, Hadi Nur,
and Mohd Nazlan Mohd Muhid and, J. of
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2, 239-244.
Nur, . Amir Faizal Naidu Abdul Manan, Lim Kheng
Wei, Mohd Nazlan Mohd Muhid and
– Halimaton Hamdan, J. of Hazardous
Materials, 117,2005, 35-40.
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