4628 Didik Prasetyoko 08. Inorganic Chemistry

The First International Seminar on Science and Technology
January 24, 2009

ISBN : 978 979 19201 0 0
Study of H-Zeolite Addition in The Esterification Step of Biodiesel Synthesis

from used Cooking Palm Oil
Karna Wijaya, Triyono and Risqi Andini
Laboratory of Physical Chemistry,
Department of Chemistry, Gadjah Mada University
Jl.Kaliurang, Km 5.5, Sekip Utara, Yogyakarta 55218
Telp./Fax.: 0274-545188
Correspondence author: karna_ugm@yahoo.com, Mobile phone: 08122692493
Abstract
It has been studied the effect of H-zeolite addition in esterifiction step of biodiesel synthesis from used
cooking palm oil using a steinlessteel biodiesel reactor with capacity of 10 L and equipped with an automatic
temperature control, a timer, and a stirrer.
The study was initiated with natural zeolite activation using technical sulfuric acid. After activation the
zeolite was characterized its acidity by gravimetric method, its structure by X-ray diffractometry, and FT-IR.
The H-zeolite then was used as solid acid catalyst in esterification step of biodiesel synthesis to decrease the
free fatty acid concentration in used palm oil. The H-zeolite which was used in the process was varied its
weight towards (oil + methanol) weight i.e. 1.50%; 3.50%; 5.50% and 6.50%. As a comparison, pretreatment
of used cooking palm oil also has been done over 1.50 % sulfuric acid. After pretreatment, the oil was
separated from methanol and H-zeolite, the reaction was continued by transesterifying the oil with methanol
using NaOH as catalyst. The transesterification product then was labeled as biodiesel. Both esterification and
transesterification process were carried out in a steinlessteel biodiesel reactor at temperature of 70oC for 2
hours. The composition of the biodiesel was analyzed using Gas chromatographyMass Spectroscopy (GCMS), 1H-NMR and their physical properties were analyzed using ASTM analysis methods.
The research results showed that activation resulted in no destruction of zeolite structure and increased its
acidity. Biodiesel reactor can used for biodiesel synthesis from used cooking palm oil. Addition of H-zeolite
in esterfication could decrease its free fatty acid content. Increasing of H-zeolite would increase the biodiesel
conversion. The highest conversion of biodiesel was 98,41% achieved by addition of H-zeolite of 5.5%
(w/w). The result of GC-MS analysis showed that main components of biodiesel were mixture of methyl
esters with methyl oleic as the major compound (40.66%). Based on the ASTM analysis data, the obtained
biodiesel specification was in agreement with diesel fuel specification for automotive.
Key words: esterification,transesterifiction, biodiesel, used palm oil, H-zeolite,
Introduction
The international demand for biodiesel and
the promotion of the oil as sources of renewable
energy which can decrease the greenhouse effect are
increasing year after year. Biodiesel can be used in
almost diesel engine when mixed with fossil diesel
oil. Biodiesel can provide benefits including:
reduction of greenhouse gas emissions and fossil fuel
use, increase rural development and a sustainable fuel
supply. However, biodiesel have some limitations
such as the feedstocks for biofuel production must be
replaced rapidly [1-10]
Biodiesel is consisting of fatty-acid alkyl
esters, known as FAME (fatty-acid methyl ester).
Fatty-acid alkyl esters are long chains of carbon
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molecules with an alcohol molecule attached to one

end of the chain. In a process called
transesterification, vegetable oils, animal fats or
restaurant greases are combined with alcohol and
chemically altered to form fatty esters such as methyl
ester [8-14]
Beside fresh vegetables oil, used cooking oil
may be used as raw material for biodiesel syntheses.
However, used cooking oil which has been heated in
high temperature usually contain high concentration
of free fatty acids. Free fatty acids will create soap
and hinder the formation of
biodiesel in
transesterification reaction step. One of the method to
deal with this is by giving a preliminary treatment on
used cooking oil in the form of an acid catalyst
adding before transesterification is conducted. The
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ISBN : 978 979 19201 0 0
purpose of the treatment is to reduce free fatty acids

concentration in used palm cooking oil through
esterification reaction. In the esterification reaction
step,usually a catalyst homogen such as sulfuric acid
was used. The use of sulfuric acid as catalyst in
industry is not considered economical because
sulfuric acid used is mixed with alcohol, so that it is
difficult to separate them, moreover sulfuric acid
which is containing sulfur can decrease the quality of
the biodiesel as fuel. As an alternative, a solid acid
catalyst such as acidified zeolite is used [13-19].
Materials And Methods

Materials
The natural zeolite was supplied by
PT.Anindya Divisi Pertambangan, Yogyakarta.
Technical grade Sodium hydroxide, methanol and
sulfuric acid were used as received. Aquabidest as a
dispersion media was purchased from Lab.of Physical
Chemistry, Gadjah Mada University. Used cooking
palm oil was purchased from CV.Kembang
Nusantara,Yogyakarta.
Where
CME
=conversion of methyl ester (%)
=integrtion value of methyl ester peaks (%)
IME
ITAG
=integration value of triasylglicerol (%)
Synthesis of Biodiesel
The H-zeolite which was used in the process
was varied its weight towards (oil + methanol) weight
i.e. 1.50%; 3.50%; 5.50% and 6.50%. As a
comparison, pretreatment of used cooking palm oil
also has been done over 1.50 % sulfuric acid. After
pretreatment, the oil was separated from methanol
and H-zeolite, the reaction was continued by
transesterifying the oil with methanol using NaOH as
catalyst. The transesterification product then was
labeled as biodiesel. Both esterification and
transesterification process were carried out in a
steinlessteel biodiesel reactor at temperature of 70oC
for 2 hours (Fig.1). The composition of the biodiesel
was analyzed using Gas chromatographyMass
Spectroscopy (GC-MS), 1H-NMR and their physical
properties were analyzed using ASTM analysis
methods.
Instrumentations
The X-Ray diffraction (XRD) patterns were
obtained
on
Shimadzu
PW3710
BASED
diffractometer equipped with Shimadzu X-ray
generator, using CuK radiation. The scanning (2)
range was from 2 to 40o and the scanning rate was
5o/min. FTIR spectra was obtained from Shimadzu
FTIR-8201 PC. Concentration of biodiesel was
determined using 1H-NMR (60 MHz) and Gas
Chromatography (HP 5890 Shimadzu), meanwhile
components of biodiesel were determined using Gas
ChromatographyMass Spectrometer (Shimadzu).
Synthesis and Characterization of H-Zeolite
The study was initiated with natural zeolite
activation using technical sulfuric acid. One hundered
gram natural zeolite with dimension of 250 mesh was
dispersed into 1,6M technical grade sulfuric acid. The
dispersion was stirred and then filtered. The solid
phase was heated at 120oC for 5 hours. The product
was labeled as H-zeolite. After activation the Hzeolite was characterized its acidity by gravimetric
method, its structure by X-ray diffractometry, and
FT-IR. To calculate methyl esters content we used
proton-NMR data and equation 1.
C ME = 100 %
5 I ME
(5 I ME ) + (9 I TAG )
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(1)
Figure.1 Biodiesel reactor with capacity of 10 L to

prepare biodiesel from used cooking plm oil
Results And Discuccion

Preparation of H-Zeolite
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The study was initiated with natural zeolite

activation using technical sulfuric acid. After
activation the zeolite was characterized its acidity by
gravimetric method, its structure
by X-ray
diffractometry, and FT-IR. From X-ray analysis result
could be concluded that the acid activation resulted in

no destruction of the natural zeolite structure
significantly. It can be seen clearly from the reflexes
of H-zeolite in its difractogram which almost all of
the reflexes still exist after acid activation (Fig.2)
Figure. 2 Difractogram of natural zeolite (above) and H-zeolit (below)
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Figure 3. FT-IR Spectra of H-zeolite (above) and natural zeolite (below)
Infra red analysis result also supported the

X-ray analysis data. There was no indication that acid
activation caused a significant distruction of zeolite
structure. After activation all importance vibrationts
of the zeolite still appeared in H-zeolite spectra
(Fig.3).
Gravimetry analysis indicated that acid
activation can cause the increasing of total acidity of
the clay in some extent (from 0.02980 mmol
NH3/gram to be 0.03125 mmol NH3/gram) . The
increase of the acid uptake indicated that the surface
area and adsorption sites of the H-zeolite was higher
than natural unmodified zeolite, Therefore, it is
expected that H-zeolite has catalytic properties higher
than natural unmodified zeolite.
Synthesis of Biodiesel
Biodiesel reactor with capacity of 10 L can
used for biodiesel synthesis from used cooking palm
oil. The product and the used cooking palm oil are
displayed in Fig.4. The color of obtained biodiesel
was bright yellow meanwhile used cooking palm oil
was dark brown. The characterization result indicated
that addition of H-zeolite in esterfication could
decrease its free fatty acid content from 4.166% to
1.58% .
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Figure 4. Used cooking palm oil (left) and biodiesel

(right)
To determine the methyl esters concentration
in product we used proton-NMR analysis method.
Analysis results (Fig.3, Fig.4.and Fig.5) exhibited that
esterification and transesterification resulted in the
formation of biodiesel which indicated by appearing a
sharp peak around 3,7 ppm at its spectrogram (Fig.
7). Calculation using equation 1 showed that the
increasing of H-zeolite would increase the biodiesel
conversion. The highest conversion of biodiesel was
98,41% achieved by addition of H-zeolite of 5.5%
(w/w).
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Figure. 5. Proton-NMR spectra of used cooking palm oil
Fig. 6. Proton-NMR spectra of esterification product
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Fig. 7. Proton-NMR spectra of biodiesel

The result of GC and GC-MS analysis
showed that main components of biodiesel were
mixture of methyl esters with methyl oleic as the
major compound ca. 40.66% (Fig. 8-12). Other

componets were methyl palmitic (34,37%), linoleic
(13,12%) and stearic (6,84%) (Fig. 9-12).
Figure.8 Chromatogram of mixed methyl esters
The existence of methyl palmitic was indicated by the

appearance of fragment with m/z= 270, 239 and 74
(Fig.9). The appearance of fragments with m/z = 294,
263, 81,55 and 41 was considered due to methyl
linoleaic (Fig. 10). Fragments with m/z = 296, 266,
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264, 74, 69, 55 and 41 was caused by methyl oleic

(Fig.11). Finally, the methyl stearic appeared with
m/z = 87, 101, 115, 129, 143, 157, 171, 185, 199,
213, 227, 241, and 225 (Fig.12).
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C3H6O2
m/z = 74
OCH3
C16H31O
m/z = 239
Figure 9. Mass spectra and structure of methyl palmitic
OCH3
C18H30O
m/z = 262
Figure 10. Mass spectra and structure of methyl linoleic
OCH3
C18H32O
m/z = 264
Figure 11. Mass spectra and structure of methyl oleic
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C3H6O2
m/z = 74
OCH3
C18H35O
m/z = 267
Figure 12. Mass spectra and structure of methyl stearic

Flash point of biodiesel from used cooking
Biodiesel produced from the above metioned
palm oil is relatively very high. The high flash point
process are further tested their physicochemical
make biodiesel easy for storing. The biodiesel can be
properties using ASTM method and are compared
saved easily and safely in tropical areas. If flash point
with the specification of ASTM biodiesel (Table 1).
of the biodiesel was lower, the biodiesel will be easily
Biodiesel resulted from esterification with H-zeolite
flammable in storing. Biodiesel from used cooking
and transesterification proved to fulfil 8 criteria
palm oil is considered to have high pour point. The
stipulated for diesel oil, which include viscosity,
high pour point cause the diesel engine to stuck in
density, flash point, water content, Conradson carbon
lower temperature so that it is not suitable for use in
residue, fuel value and specific density. Viscosity of
sub tropical areas.
biodisel is related to specific density in which the
The comparison between specification of
higher the viscosity was, the greater the specific
biodiesel produced in the research with specification
density would be. Biodiesel with high specific density
of diesel oil for industry and automotive was shown
will be difficult to flow so that it will slow down the
in Table 1. Of the five criteria presented, our
ignition process. Biodiesel viscosity from used
biodiesel fulfil the requirements for being alternative
cooking palm oil had lower viscosity than used oil,
fuel for diesel oil for industry and auttomotive.
and if it is used as fuel for diesel engine, the result of
injection in ignition chamber will easily form nebula
which facilitate ignition.
Table 1. Comparison between physical characteristic of biodiesel with diesel oil for industry
and automotive diesel oil.
Parameter
Specific density 60/60 oF
Brutto fuel value (GHV),
BTU/lb **)
Netto fuel value (NHV),BTU/lb **)
Kinematic viscosity 40oC
Pour point, oF
Flash point, oF
Conradson carbon residue %
Water content, % vol.
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Used cooking
palm oil
0,9124
Automotive diesel
oil*)
0,820-0,870
Industry
diesel oil*)
0,840-0,920
19173,25
19031-19220
18842-19145
17423,52
40,37
39,2
341,6
0,391
0,12
17856-17977
2,0-5,0
65,000
Min 150
Max 0,100
Max 0,05
17735-17929
7,000
65,000
Min 150
Max 1,000
Max 0,05
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Conclusions
The research results showed that activation
resulted in no destruction of zeolite structure and
increased its acidity. Biodiesel reactor can used for
biodiesel synthesis from used cooking palm oil.
Addition of H-zeolite in esterfication could decrease
its free fatty acid content. Increasing of H-zeolite
would increase the biodiesel conversion. The highest
conversion of biodiesel was 98,41% achieved by
addition of H-zeolite of 5.5% (w/w). The result of
GC-MS analysis showed that main components of
biodiesel were mixture of methyl esters with methyl
oleic as the major compound (40.66%). Based on the
ASTM analysis data, the obtained biodiesel
specification was in agreement with diesel fuel
specification for automotive.
References
1.
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3.
4.
5.
6.
7.
8.
Arrowsmith, C.J., J. Ross, 1945, Treating

Fatty Materials, US Patent , 2,383,580.
Canakei, M., dan Van Gerpen, J., 2003, A
Pilot Plant to Produce Biodiesel from High
Free Fatty Acids Feedstocks, Am. Soc.
Agric, Eng., 46, 945-954.
Demirbas, A., 2003, Biodiesel Fuels from
Vegetable Oils via Catalytic and NonCatalytic
Supercritical
Alcohol
Transesterifications and Other Methods: A
Survey, J. Tur. Chem. Educ., 44, 2093-2109.
Freedman, B., 1984, Variables Affecting the
Yield of Fatty Aster from Transesterified
Vegetables Oil, J: Am. Oil Chem, 10,61.
Hamdan, H., 1992, Introduction to Zeolites:
Synthesis,
Characterization,
and
Modification,
Universiti
Teknologi
Malaysia, Kuala Lumpur.
Hanna, A.M., dan Ma, F., 1999, Biodiesel
Production Areview, J., Agric & Natural, 70,
1-15.
Hardjono, A., 2001, Teknologi Minyak Bumi,
Edisi pertama, Gadjah Mada University
Press, Jogjakarta.
Hidayat, D, 2008, Pengaruh katalis H-Zeolit
pada Proses Pembuatan Biodiesel dari
Minyak Jelantah kelapa Sawit Bekas
Menggunakan
Reaktor
Biodiesel
berkapasitas 10 L, Skripsi, Universitas
Gadjah Mada, Jogjakarta.
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Houas, A. Lachleb, H., Puzenut, E., Ksibi,

M., Elaleui, E., Gullard, G., and Hermann,
J.M., 2001, Photocatalytic Degradation
Pathway of Methylene Blue in Water, Appl.
Catal. B: Environmental 30. 145-157.
Keim, G.I., 1945, Treating Fats and Fatty
Oils U.S., Patent, 383.
Knothe, G., 2000, Monitoring a Progressing
Transesterification Reaction by Fiber-Optic
Near Infrared Spectroscopy with correlation
to H Nuclear Magnetic Resonance
Spectroscopy, Jpn. Am. Oil. Chem. Soc., 77,
J 9483, 489-493.
Mastutik, D., 2006, Transesterifikasi Minyak
Jelantah Kelapa Sawit menjadi Biodiesel
Menggunakan Zeolit-Y Melalui Proses
Esterifikasi, Tesis, Universitas Gadjah
Mada, Jogjakarta.
Nye, M.J., dan southwell, P.H., 1983, Esters
from Repeseed Oil as Diesel Fuel In: Proc.
Vegetable Oil as Fuel Seminar III, Pcoria:
Northern Agricultural Energy Center, 78-83.
Oudejans, J.C., 1984, Zeolite Catalysis in
Some
Organic
Reactions,
Chemical
Research (SON), Holland.
Patzer, R., dan Norris, M., 2002, Evaluated
Biodiesel Made from Waste Fats and Oils,
Final
report,
Agriculture
Utilization
Research Institute, University of Minnesota,
Minnesota.
Saefudin, A., 2005, Sintesis Biodiesel
Melalui reaksi esterifikasi Minyak Jelantah
Dengan Katalis Montmorillonit Teraktivasi
Asam Sulfat Yang Dilanjutkan Dengan
Reaksi Transesterifikasi Terkatalisis NaOH,
Skripsi,
Universitas
Gadjah
Mada,
Jogjakarta.
Setyawan, D.A., 2001, Pengaruh Waktu dan
temperatur
Hidrotermal
terhadap
Dealuminasi dan Keasaman Zeolit Alam
Aktif, Skripsi, FMIPA UGM, Yogyakarta.
Van, Gerpen, J., Shanks, B., Pruszko, R.,
2004, Biodiesel Production Technology,
National Renewable Energy Laboratory,
Collorado.
Zappi, M., Hernandez, M., Spark, D., Horne,
J., Brough, M., 2003, A Review of the
Engineering Aspects of the Biodiesel
Industry, MSU Environmental Technology
Research and Applications Laboratory Dave
C. Swalm School of Chemical Engineering
Mississippi State University, Mississippi.
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Preparation of Solid Acid Catalysts from Bentonite and Their Catalytic

Activities for The Esterification of Jatropha curcas Seed Oil
Novizar Nazir1,3, Djumali Mangunwidjaja2, Mohd. Ambar Yarmo3 Jumat Salimon3
and Nazaruddin Ramli3
1
Faculty of Agricultural Technology, University of Andalas Padang, Indonesia

Kampus Limau Manis. Padang 25163, Indonesia
Telp. +62 751 72772- E-mail address: nazir_novizar@yahoo.com
2
Department of Agroindustrial Technology, Institut Pertanian Bogor
Kampus IPB Darmaga, Bogor, Indonesia
3
School of Chemical Science and Food Technology, FST UKM, Malaysia
43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia
Abstract
The esterification reaction of Jatropha curcas seed oil with methanol to remove free fatty acid (FFA)
for biodiesel production was conducted using various bentonite catalysts. Solid acid catalysts from
bentonite were prepared by aqueous impregnation technique. 5.3 M HCl and 40% by mass of H2SO4
were supported on bentonite by aqueous impregnation, washed with deionized water till Cl-1 and SO42
ions were not detected, dried overnight and calcinated at 500 oC for three hours. Catalysts was
characterized by XRD, nitrogen adsorption-desorption, and pyridine adsorption FTIR. Five catalysts
used in esterification reactions of Jatropha curcas seed oil with methanol were compared: (A) nonactivated bentonite; (B) HCl 5.3 M-activated bentonite; (C) HCl 5.3 M-activated bentonite and
calcinated at 500 oC (D) H2SO4 40%-activated bentonite; (E) H2SO4 40%-activated bentonite and
calcinated at 500 oC. The effects structure properties of bentonite catalysts were discussed relating
to the conversion of the FFA.
Keywords:
biodiesel
Jatropha curcas, solid acid catalyst, esterification, acid-activated bentonite, FFA,
Introduction
With the increasing price of petroleum and
environmental concerns over pollution caused by the
internal combustion gases, alternative fuels have been
developed [1, 2]. Biodiesel is considered as one of the
alternative fuels for diesel engines become
increasingly important [3].
Biodiesel is defined as the mono alkyl esters of
long chain fatty acids derived from renewable
feedstocks, such as vegetable oil or animal fats, use in
compression ignition engine [4]. It is a clean-burning
fuel, biodegradable, nontoxic and has low emission
profiles and so is environmentally beneficial. Use of
biodiesel has the potential to reduce the level of
pollutants and of potential carcinogens [5,6,7].
In biodiesel production, the use of edible oils will
compete with the food product. Consequently, the
use of non-edible oil as alternative source will be
important. Among several non-edible oil seed species
could be utilized as source for oil production, J.
curcas which grows in tropical and sub-tropical
climates accross developing world is a multipurpose
species with many attributes and potentials [8,9]
However, the relatively higher amounts of free fatty
Proceeding Book
acids (FFA) and water in this feedstock results in the

production of soap in the presence of alkali catalyst.
During alkaline-catalyzed transesterification, high
content FFA will react with alkali catalysts to produce
soaps which will inhibit the transesterification for
biodiesel production. Furthermore, the large amount
of soap can gel and also prevent the separation of the
glycerol from the ester [5].
Acid-catalyzed
transesterification, despite its insensitivity to FFA in
the feedstock, has been largely ignored mainly
because of its relatively slower reaction rate [6].
Therefore a process combining pretreatment with
alkaline-catalyzed transesterification for feedstocks
having high FFA content was investigated by many
authors [10,11,12,3].
Acid-catalyzed esterification of high FFA content
vegetable oils is a typical method of biodiesel
production due to high reaction speed and high yield
[13]. Some raw feedstocks with high FFA such as
yellow and brown grease [10], rubber seed oil [11]
mahua oil [14], waste cooking oil [15] and jatropha
oil [11] have been used to produce biodiesel with
homogeneous acid-catalyzed esterification followed
by transesterification using alkaline catalyst.
Compared with conventional liquid acid catalysts,
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solid acid catalyst is more environmentally friendly

[15].
The present work was undertaken to investigate
the pretreatment process for reducing the FFA content
of jatropha oil for biodiesel production using various
bentonite as solid acid catalyst. This paper focuses on
the reaction parameters that affect the conversion of
FFA in crude jatropha oil by means of acid-catalyzed
esterification with methanol.
Materials and Methods

Materials
Jatropha curcas oil was hydrolic press extracted of
jatropha seed from Lampung, South Sumatra,
Indonesia. Anhydrous methanol (MeOH), 99.8%,
potassium hydroxide (KOH), sulfuric acid (H2SO4),
and Hydrochloric acid (HCl), 37-38% pure were
purchased from ChemAR.
A calcium-rich bentonite (CaB) sample was
obtained as powder from PT. Superintending
Company of Indonesia used in the experiments. The
bulk chemical analysis of the bentonite (mass %) is
SiO2, 64.15; TiO2, 0.47; CrO3, 0.003; Al2O3,.70;
Fe2O3, 0.10; MgO, 0.70; CaO, 0.03; , Na2O, 0.20;
K2O, 0.50 and loss on ignition (LOI), 22.61.
Preparation of Catalyst [16,17]
Acid-activated Bentonite were prepared by
aqueous impregnation technique. 5.3 M HCl and
40% by mass of H2SO4 were supported on bentonite
by aqueous impregnation (at 80 oC and 4 h), washed
with deionized water till Cl-1 and SO4-2 ions were not
detected, dried overnight and calcinated at 500 oC for
three hours. Five catalysts for esterification of
jatropha oil with methanol were compared: (A)
untreated bentonite catalyst; (B) esterification with
5.3 M HCl-activated bentonite catalyst; (C)
esterification with 5.3 M HCl-activated bentonite and
calcinated at 500 oC catalyst (E) esterification with
40% H2SO4-activated bentonite catalyst; (F)
esterification with 40% H2SO4-activated bentonite
and calcinated at 500 oC catalyst.
Characterization of Catalyst
The X-ray diffraction (XRD) patterns of natural
and acid activated samples were recorded from
random mounts prepared by glass slide method using
a Rikagu D-Max 2200 Powder Diffractometer,
operating at 40 kV and 30 mA, using Ni-filtered
CuKa radiation having 0.15418 nm wavelength, at a
scanning speed of 2o2 min_1. Surface area of
bentonite was measured with multipoint Brunauer,
Emmett and Teller (BET) method from the
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Quantachrome
Surface
Analysis
Instrument
(Autosorb 1-C, Boynton Beach, Florida, USA). This
was done using nitrogen adsorption/desorption
isotherms at liquid nitrogen temperature and relative
pressures (P/Po) ranging from 0.04- 0.4 where a
linear relationship was maintained. For acidity study,
about 10 mg of the sample was pressed at 2-5 tonnes
for a minute to obtain a 13 mm disk. The sample was
introduced in infrared cell with calcium flourite.
Each sample was degases for 16 hours under vacuum
at 400 C. The infrared spectra were collected at
room temperature using Simadzu 2000 FTIR
spectrometer at 2 cm-1 resolution. The type of acid
sites were examined using pyridine as probe
molecule. Then pyridine was absorbed for 30
seconds at room temperature, continued by desorption
at 150 C for 1 hour. Finally, the sample was
desorpted at 400 C for 1 hour.
Esterification process catalyzed by sulfuric acid
Esterification was conducted in a 250 ml threeneck flask.
The flask was equipped with a
mechanical agitator and a reflux condenser, and
heated with a water bath to control the reaction
temperature (60oC). In the experiments, flasks loaded
with Jatropha oil samples were firstly heated to the
designated temperature. This was followed by the
addition of the methanol (methanol : oil ratio, 0.28
v/v) and sulfuric acid (1.34%) mixture before turning
on the agitator, marking the start of the esterification
reaction.
The application solid acid catalyst in esterification
process
Esterification was conducted in a 250 ml threeneck flask. In the experiments, flasks loaded with
Jatropha oil samples were firstly heated to the
designated temperature (60oC). This was followed by
the addition of the methanol (methanol : oil ratio, 0.30
v/v) and solid acid catalyst (5% w/v oil) mixture
before turning on the agitator, marking the start of the
esterification reaction. The esterification products
were separated in a tap funnel to obtain the upper oil
layer. After methanol recovery under vacuum at
50oC, oil layer was then washed with water several
times until the pH of washing water was close to 7.0.
The resultant esterified oil was dried by anhydrous
magnesium sulfate before acid value analysis.The
convertion of FFA was defined as the fraction of the
FFA removed. The convertion of FFA (xFFA) was
determined from acid number ration using below
equation [15]:
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Where ai is the initial acid number of the reactant

and at is the acid number of product at t time.
2500
Alkali catalysed transesterification of jatropha oil

2000
The collected oil layer was transferred to 250 ml

round bottom, 0.1g v/v methanol and 3.5 w/v +acid
number of KOH were added. The mixture was
reacted for 24 minutes at 65oC. The mixture was left
to settle to separate into two layers. The upper layer
was the FAME (crude biodiesel).
1500
1000
Results and Discussion
HCl5.3. M non-calicinated
500
Characterization of Catalyst
Fig. 1 shows changes in intensity and width of
the 001 peak, which indicate that the crystallinity of
the bentonite is considerably affected by acid
activation an calcination. The variation of relative
intensity (I / I0) and full width at half-maximum
(FWHM) peak height of the XRD peak for bentonites
represent the intensities for the natural and acidactivated bentonite samples, respectively. The
decrease in I / I0 and increase in FWHM on the 001
XRD peak show that the crystallinity of bentonite
decreases by increasing in acid [17].
0
0
0
10
15
o2
20
30
35
Fig. 1. The XRD patterns of the natural and some of

the acid-activated bentonite (S: smectite, I:
illite, FWHM: full width at half maximum
peak height).
The total pore volume of samples is measured by
condensation of N2 adsorbate at P/Po 0.95 in the pores
of diameter <400 by single point method (Table 1).
Fig.2 shows the FTIR spectra of bentonites after
pyridine adsorption at room temperature for 30
seconds (a) and after pyridine adsorption and
desorption at 150 oC for 1 h (b). It is shown that the
spectra
of
samples
are
not
similar.
Table 1 Physical parameter of bentonite and acid-activated bentonites.

Physical parameter
Catalyst
A
B
C
D
BET surface area (m2/g)
50.6496
239.3534
210.1829
248.3601
Langmuir surface area(m2/g)
79.1939
374.8640
329.6299
389.3721
External surface area (m2/g)
46.6242
226.2408
199.0738
233.6701
Micropore area (m2/g)
4.0254
13.1128
11.0990
14.6900
Micropore volume (m3/g)
0.0018
0.0052
0.0044
0.0060
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25
E
252.2536
393.8833
232.8391
19.4145
0.0085
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[a]
[b]
Fig. 2. FTIR spectra of samples (a) after pyridine adsorption at room temperature for 30 seconds, (b) after
pyridine adsorption and desorption at 150 oC for 1 h.
Effect of esterification reaction time and type of
bentonite to acid value
The effect of esterification reaction time and
type of bentonite to acid value is shown in Fig.3.
The results show that the acid value decrease
significantly after 6 hours esterification. The best

catalyst is HCl-activated bentonite without
calcination with 67.70% FFA convertion after six
hours reaction time. This result is lower than
heterogeneous catalyzed reaction of H2SO4
(91.70% FFA convertion).
Fig.3. Effect of esterification reaction time and type of bentonite to acid value of esterified oil
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Effect of esterification reaction time to convertion

of FFA and acid value
According to Lu et al [18], FFA convertion
will increase with the increasing of time,
temperature and ratio methanol to oil. In this
experiment we increase the reaction temperature
from 60oC to 65oC and methanol to oil ratio from

0.30 (v/v) to 0.40 (v/v) using catalyst B. The
convertion of FFA and acid value of esterified oil is
shown in Fig.4. The result shows that the
convertion of FFA increase from 67.70% to 81.7%
Fig. 4. Effect of esterification reaction time to convertion of FFA and acid value of esterified oil
Alkali catalysed transesterification of jatropha oil
In this work, the lowest acid value of esterified
jatropha oil was 2.32 mg KOH/g. In fact, the alkali
catalyzed transesterification of jatropha oil could
work, even if the FFA content was over 1% [19].
The reaction of jatropha oil with methanol was easy
to perform. The bottom layer of glycerol was

obvious after 24 minutes reaction time [12].
Chemical properties of jatropha biodiesel obtained
from the FFA removal by esterefication of FFA in
jatropha oil with H2SO4 (at 60 oC and 88 minutes
reaction time) and HCl-activated bentonite (at 70
o
C and 6 hours reaction time) is shown in Table 2.
Table 2. Chemical properties of jatropha biodiesel obtained from the FFA removal by esterefication of FFA in
jatropha oil with H2SO4 (at 60 oC and 88 minutes reaction time) and HCl-activated bentonite (at 70
o
C and 6 hours reaction time)
Property
Product after the
Product after the
reaction on H2SO4 reaction on HClactivated bentonite
Density (kg/m2)
0,87
0,87
Kinematic viscosity (mm/s2)
1,73
1,74
Free Fatty Acid (mg KOH/g oil)
0,24
0,47
Conclusion
Based on the result of this study, it can concluded
that:
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1. Acid activation and calcination on bentonite

affect the cristalinity, surface area, pore
volume and acidity properties of bentonite.
2. HCl-activated bentonite without calcination has
potential to be solid acid catalyst for
esterification of jatropha oil. Convertion of
FFA reached 81.7% when parameters are as
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follows: reaction time 6 h, amount of catalyst

5%, ratio methanol oil 0.4 v/v and reaction
time 65oC.
3. HCl-activated bentonite as acting as
heteregeneous acid catalyst shows good
activity to catalyze the esterification of
jatropha oil and methanol. Compared with
sulfuric acid, this catalyst is environmentally
friendly, easy to separate from the system,
reusable and does not need high cost
equipment for anti-corrosion
Acknowledgements
The authors thank University Kebangsaan Malaysia
for all facilities and supporting this study by the
Research University Grant UKM-oup-nbt-29151/2008.
References
[1]
[2]
[3]
[4]
[5]
[6]
M. Fangrui,
A.H. Milford (1999):
Biodiesel production: a review. Bioresour.
Technol. 70, 115.
J.M. Marchetti, V.U. Miguel, A.F. Errazu
(2007).
Possible methods for biodiesel
production, J. Renew. Sustain. Energy Rev. ,
11, 13001311.
H.J. Berchmans,., and S. Hirata (2008).
Biodiesel production from Jatropha curcas
L. Seed oil with a high content of free fatty
acids. Bioresour. Technol. 99, 1716-1721.
L.C Meher, V.D. Sagar, S.N. Naik (2006)
Technical aspects of biodiesel production by
transesterificationa review,
J.Renew.
Sustain. Energy Rev. 10, 248268.
A.Demirba (2002).
Biodiesel from
vegetable oils via transesterification in
supercritical methanol, Energy Conserv.
Manage. 43, 23492356.
Y. Zhang, M.A. Dub, D.D. McLean, M.
Kates (2003). Biodiesel production from
waste cooking oil: 1. Process design and
technological assessment. Bioresour. Techn.
, 89, 1-16.
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Synthesis and Characterization of Al2O3/TS-1

Rivone Septa Wijayanti, Didik Prasetyoko
Laboratorium of Inorganic Chemistry, Department of Chemistry, Faculty of Mathematic and Sciences, Institut
Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia.
1)
Corresponding author, Phone: +62-31-5943353
email: didikp@chem.its.ac.id
rivone_sw@yahoo.com
Abstract
TS-1 has good catalytic activity in reaction of selective oxidation of organic materials such as
benzene and phenol using H2O2 as oxidizing agent. However, it has hydrophobic character that
correlate with the slow rate of the reaction. Modification of catalyst using metal oxide result in
decreased of hydrophobic property, and as a sonsequence the rate of the reaction will be
increased. In this paper, TS-1 was modified by Al2O3 using impregnation method. The solid
were characterized by X-ray diffraction, infrared spectroscopy, and hydrophilicity techniques.
Hydrophilicity test of Al2O3/TS-1 was carried out using the mixture of xylene and water. The
impregnated catalysts Al2O3/TS-1 show partially hydrophilic property. Al2O3/TS-1 catalyst with
4%wt loading demonstrated fastest submerged time at water as compare to other samples. The
addition of Al2O3 increased hydrophilicity of TS-1 which is indicated by the results of
hydrophilicity test.
Key words: catalyst, Al2O3/TS-1, hydrophilic
Introduction
The synthesis of titanium silicalite (TS1) was first reported by Taramasso et al. [1] in
1983. Titanium silicalite-1 (TS-1), a MFI-type
titanosilicate, has been used as a highly-efficient,
heterogeneous catalyst for selective oxidation of
organic compounds using hydrogen peroxide as an
oxidant. TS-1 can lessens tar product and side
products which have potential as pollutant [2]. Over
the last decade, the literature has reflected a high
activity and selectivity of H2O2 on TS-1 as catalysts
for mild oxidation reactions with H2O2 used as the
oxidant, such as phenol hydroxylation, olefins
epoxidation,
cyclohexanone ammoximation,
alkane oxidation, oxidation of ammonia to
hydroxylamine,
secondary
amines
to
dialkylhydroxylamines [3].
TS-1 has been commercialize in
hydroxylation reaction of phenol with high
hydroquinone selectivity and high H2O2 efficiency
[4]. Hydroxylation reaction of phenol to produce
diphenol had draws many attention since 1970s,
and some catalysts either homogen and also
heterogeneous have been applied in this reaction
[5].
Reaction
mechanism
of
phenol
hydroxylation is as follows (1) TS-1 will
decompose H2O2 (oxidation agent) which has
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hydrophilic character to form titanium-peroxo

radical (initiation step), then (2) propagation step in
solution [2]. This mechanism can be explained via
titanium-peroxo complex formation mechanism as
intermediate from reaction between H2O2 and TS-1
catalyst [6-10]. The rate of the forming of titaniumperoxo depended on the rate of H2O2 reach to active
site in TS-1. H2O2 is hydrophilic, that is quiet
different from hydrophobic character of TS-1. [11],
consequently the reaction rate of phenol
hydroxylation reaction is tends to be slow [7].
One of the way to increase phenol
hydroxylation reaction rate by modifieng of catalyst
TS-1. Hence the existence of modified catalyst will
influence its the character of chatalytic. The
property of TS-1 modified properties made become
more hydrophilic character by increasing acidity.
The addition of metal oxide is the way to increase
acidity, so the reaction rate of H2O2 with TS-1 to
forms Ti-peroxo becomes more quicker. The
addition of acidity character may come from Lewis
acidity site or Brnsted acidity site. In this research
applied Al2O3/TS-1 having acidity side of Lewis
which is high as metal oxide added at TS-1. So that
also can increase reaction rate of H2O2 with TS-1 to
forms Ti-Peroxo which in the end will yield
product briefer. Finally the reaction rate of phenol
hydroxylation at Al2O3/TS-1 will be much faster
and shows increasing of catalytic activity and
selectivity higher than TS-1.
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Material and Methods

For TS-1 (1 mol% of Ti), tetraethyl
orthosilicates, TEOS (Merck, 98%) was placed into
a Teflon beaker and vigorously stirred, tetraethyl
orthotitanate, TEOT (Merck, 95%) was carefully
added dropwise into this TEOS. The beaker was
covered with parafilm to avoid hydrolysis. The
temperature of the mixture was raised to 35oC and
the reactants were mixed homogeneously for half
an hour. Then the mixture was cooled to about 0oC.
The solution of TPAOH (Merck, 20% TPAOH in
water), which was used as template, was also
cooled to 0oC.
After a few minutes, TPAOH was added
drop-wise slowly into the mixture of TEOS and
TEOT. At first, one should wait a few minutes after
addition of a few drops of TPAOH solution before
more TPAOH solution is added, to avoid
precipitation. Stirring and cooling were continued
during this process. After the addition of about 10
mL the addition rate of TPAOH solution was
increased. When the addition of TPAOH was
completed, the mixture was heated in the
temperature range of 80-90oC for about 4 h in order
for the hydrolysis of TEOS and TEOT to take
place. Distilled water was added to increase the
volume of the mixture, after which a clear gel was
obtained. The gel was transferred into autoclave
and heated at 175oC under static condition. The
material was recovered after 4 days of
hydrothermal crystallization by centrifugation and
washing with excess distilled water. A white
powder was obtained after drying in air at 100oC
overnight. The calcination of the sample to remove
the template was carried out under static air at
550oC for 5 h with temperature rate at 1o/min.
Samples
of
Al2O3/TS-1
catalyst
containing 0,5%; 1%; 2%; and 4% were prepared
by impregnation method, titanium silicalit (TS-1)
was added to alumunium (III) nitrate solution
which obtained by dissolving alumunium (III)
nitrat. This mixture stirred at 80C for 3 h, dried at
80-90C to eliminate water, and calcined at 550C
for 5 h. Catalyst TS-1 and Al2O3/TS-1 were
characterized by X-ray diffraction (XRD) and
infrared spectrum is recorded with FourierTransform Infrared (FT-IR) spectrophotometer,
with KBr palette method. Hidrophilicity properties
of samples was analyzed by catalyst sample powder
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dispersion method at water phase and organic phase

mixture (water and xylene). The movement of
catalyst sample at each phase was observed.
Result and Discussion

Structural and phase of samples were
determined by X-ray diffraction. The XRD patterns
were showed in figure 1. Characteristic diffraction
line of TS-1 is observed at 2 = 7.88; 8.78; 23.14;
23.9; 24.39; 2478. The peak at 2 around 24 is
observed for the change of crystal symmetry from
monoclinic symmetry, which is symmetry of
silicalit-1, becomes orthorombic symmetry which is
symmetry of TS-1. This Phenomenon indicates that
titanium atom is in the framework structure of TS-1
[12].
X-ray
diffraktogram
pattern
of
Al2O3/TS-1 with various Al2O3 loading variation at
TS-1, showed similar pattern. XRD pattern of
Al2O3/TS-1 with various of Al2O3 loading showed
similar pattern with parent sample TS-1 shown in
figure 1. Main top of crystal TS-1 emerges at 2 =
7.88; 8.78; 23.14; 23.9; 24.39; 24.78. The similar
pattern of XRD Al2O3/TS-1 indicates that Al2O3
dispersed at surface of titanium silikalit-1.
Therefore, the low content of Fe2O3 (up to 4 %wt)
on TS-1 catalyst surface doesn't change the initial
structure framework of TS-1.
This finding indicated that the MFI
structure of TS-1 is not collapsed after
impregnation of Al2O3.
Catalyst samples of TS-1 and Al2O3/TS1 showed absorption band at around 1100, 800, and
450 cm-1, which is vibration mode of SiO4 or AlO4
tetrahedral [13]. Absorption band at around 1100
cm-1 is unsimmetrical vibration mode of Si-O-Si,
and absorption band at around 800 cm-1 is its
symmetrical vibration mode. Absorption band
appeared at around 1230 and 547 cm-1. It is
characteristic of tetrahedral structure in framework
zeolite MFI [14]. Absorption band appeared at
around 970 cm-1 is characteristic of TS-1 which is
vibration mode of stretching Si-O from unit [SiO4]
which tied at atom TiIV with tetrahedral
coordination in TS-1 framework. Absorption band
appear at this wavenumber is evidence that titanium
atom has stayed in framework catalyst [15].
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4 Al2O3/TS-1
2 Al2O3/TS-1
1 Al2O3/TS-1
0,5 Al2O3/TS-
TS-1
Figure 1 X-ray powder patterns of samples TS-1 and Al2O3/TS-1 with various loading
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4Al2O3/TS-1
1100 cm-1
1230 cm-1
450 cm-1
1Al2O3/TS-1
547 cm-1
800 cm-1
970 cm-1
2Al2O3/TS-1
0.5Al2O3/TS-1
TS-1
Figure 2 Framework IR Spectra of samples TS-1 and Al2O3/TS-1 with various loading
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Table 1. Hydrophilicity Character Definition

Sample pass submerged the interfacial phase into water as a whole and
quickly
Hydrophilic
Hydrophilic
Sample pass submerged interfacial phase into water not fairly quickly
but in the end all sample is submerged sample
Hydrophilic
Initially sample tantalum at interfacial phase and then immerses in

water slowly and as a whole
Initially sample tantalum at interfacial phase, then some particle will
submerged into water slowly and some tantalum particles at interfacial
phase, after squealer, all sample is immerses in water
Initially sample tantalum at interfacial phase, after squealer, some
particles there are still tantalum at interfacial phase
Sample will be tantalum permanently at interfacial phase though after
squealer is done
Partially Hydrophilic
Partially Hydrophobic
Perfect Hydrophobic
Sample
TS-1
0,5Al2O3/TS-1
1Al2O3/TS-1
2Al2O3/TS-1
4Al2O3/TS-1
Tabel 2. Hydrophilicity Character of TS-1 dan Fe2O3/TS-1

Index
Character
Water sumerged time
(seconds)
5
1 minutes 10 second
5
42 second
5
38 second
5
30 second
5
28 second
Hydrophilic test of sample was carrying

out using mixture xylen and water [16]. The result
of hydrophilic characterization test of sample is
given at tables 2.
Table 2 gives an information about
hydrophilicity properties of catalyst samples. Ts-1
sample has hydrophobic character. This result is
similar with the research that had been carried out
by Drago [14]. This phenomena is caused by the
structure of TS-1 which active site Ti tetrahedral is
isolated
Presence metal oxide at TS-1, character
of hydrophilic increased. This thing proves that
with presence Al2O3 increased hydrophilicity side
of TS-1 which is indicated from increases Lewis
side acid.
Conclusion
1.
2.
3.
Catalyst TS-1, 0,5% Al2O3/TS-1, 1%

Al2O3/TS-1, 2% Al2O3/TS-1, and 4%
Al2O3/TS-1 has successfully synthesized.
The addition of Al2O3 at TS-1 doesn't change
crystal structure TS-1 with zeolite type MFI.
Catalyst sample TS-1 and Al2O3/TS-1 shows
absorption band at around 1100, 800, and 450
cm-1, which is vibration mode of SiO4 or AlO4
tetrahedral. This spectra is characterization of
MFI.
Proceeding Book
4.
With existence of addition of Al2O3 at TS-1,

character of hydrophilic increased. Al2O3/TS1 4% loading gives submerged time at fastest
water compare to other sample.
Acknowledgements
References
[1] Taramasso, M., Perego, G. and Notari, B.
(1983), Preparation of Porous Crystalline
Synthetic Material Comprised of Silicon and
Titanium Oxides.
(U. S. Patents No.
4,410,501).
[2] Kurian, M., Sugunan, S. (2006), Wet Peroxide
Oxidation of Phenol Over Mixed Pillared
Montmorillonites, Chemical Engineering
Journal, Vol. 115, pp. 39-146.
[3] Liu, X., Wang, X., Guo, X., Li, G. (2004),
Effect of Solvent on the Propylene
Epoxidation over TS-1 Catalyst, Catalysis
Today, Vol. 93-95, pp. 505-509.
[4] Choi, J., Yoon, S., Jang, S., Ahn, W. (2006),
Phenol Hydroxylation Using Fe-MCM-41
Catalysts, Catalysis Today, Vol. 111, pp. 280287.
[5] Tang, H., Ren, Y., Yue, B., Yan, S., He, H.
(2006),
Cu-incorporated
Mesoporous
Materials : Synthesis, Characterization and
Catalytic Activity in Phenol Hydroxylation,
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ISBN : 978 979 19201 0 0
Journal of Molecular Catalysis A : Chemical,

Vol. 260, pp. 121-127.
[6] Vayssilov, G. N. dan van Santeny, R. A.
(1998), Catalytic Activity of Titanium
Silicalitesa DFT Study, Journal of
Catalysis, Vol. 175, pp. 170174.
[7] Sun, J., Meng, X., Shi, Y., Wang, R., Feng, S.,
Jiang, D., Xu, R., Xiao (2000), A Novel
Catalyst of CuBiVO Complex in Phenol
Hydroxylation with Hydrogen Peroxide,
Journal of Catalysis, Vol. 193, pp. 199206.
[8] Wilkenhner, U., Langhendries, G., van Laar,
F., Baron, G. V., Gammon, D. W., Jacobs, P.
A., dan van Steen, E. (2001), Influence of
Pore and Crystalline Titanosilicates on Phenol
Hydroxylation in Different Solvents, Journal
of Catalysis, Vol. 203, pp. 201-212.
[9] Bonino, F., Damin, A., Ricchiardi, G., Ricci,
M., Spano`, G., DAloisio, R., Zecchina, A.,
Lamberti, C., Prestipino, C., dan Bordiga, S.
(2004), Ti-Peroxo Species in The TS1/H2O2/H2O System, Journal of Physical
Chemistry B, Vol. 108, pp. 3573-3583.
[10] Liu, H., Lu, G., Yanglong Guo, Yun Guo, dan
Wang, J. (2006), Chemical Kinetics of
Hydroxylation of Phenol Catalyzed by TS1/Diatomite in Fixed-Bed Reactor, Chemical
Engineering Journal, Vol. 116, pp. 179186.
[11] Armaroli, T., Bevilacqua, M., Trombetta, M.,
Milella, F., Alejandre, A. G., Ramirez, J.,
Notari, B., Willey, R. J., dan Busca, G. (2001),
A Study of The External and Internal Sites of
MFI-Type Zeolitic Materials through The
FTIR Investigation of The Adsorption of
Nitriles, Applied Catalysis A : General, Vol.
216, pp. 5971.
[12] Li, Y.G., Lee, Y.M., Porter, J.F. (2002), The
Synthesis and Caracterization of Titanium
Silicalite-1, Kluwer Academic Publishers, pp.
0022-2461.
[13] Flanigen. E. M. (1976). Structural analysis by
infrared spectroscopy. In: Rabo, J. A. ed.
Zeolite chemistry and catalysis. ACS
Monograph Vol. 171; pp. 80-117.
[14] Drago, R., Dias, S. C., McGilvray, J. M.,
Mateus, A. L. M. L., 1997, Acidity and
Hidrophobicity of TS-1, Journal Physic
Chemistry B, vol. 102, pp. 1508-1514.
[15] Li, G., Wang, X., Guo, X.,Liu, S., Zhao, Q.,
Bao, X., Lin, L. (2001), Titanium Species in
Titanium Silicalite TS-1 Prepared By
Hydrothermal Method, Materials Chemistry
and Physics, Vol. 71, pp. 195-201.
[16] Wang, Z., Wang, T., Wang, Z., Jin, Y. (2004),
Organic Modification of Ultrafine Particles
using Carbon-dioxide as the Solvent, Journal
of Powder Technology, Vol. 139, pp. 148-155.
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Synthesis and Characterization of Fe2O3/TS-1 Catalyst

Cholifah Endahroyani, Didik Prasetyoko
Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia
email: didikp@chem.its.ac.id
Abstract
Hydroxylation reaction of phenol into diphenol, such as hydroquinone and cathecol, has a great role
in many industrial applications. Phenol hydroxylation reaction has been carried out by using Titanium
Silicalite (TS-1) as catalyst and H2O2 as an oxidant. TS-1 catalyst has high activity and selectivity for
phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward
the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be
low. Addition of metal oxide can enhanced hydrophilicity character of TS-1 catalyst. In this research,
TS-1 catalyst was modified by addition of metal oxide Fe2O3 by impregnation method. Fe2O3/TS-1
catalyst were characterized by X-ray diffraction, FT-IR spectroscopy and hydrophilicity analysis
techniques. The new catalyst, Fe2O3/ TS-1 showed higher hydrophilicity compared to TS-1, and it can
be predicted that the reaction rate of phenol hydroxylation will be much faster and will be showed
increasing of catalytic activity and selectivity than that of parent catalyst, TS-1.
Key words: catalyst, TS-1, Fe2O3/ TS-1, hydrophilic site, phenol hydroxylation
Introduction
Hydroxylation reaction of phenol to
produce diphenol (catechol and hydroquinone) and its
isomers is one of important reaction because phenol
has various important functions such as antioxidant,
polymerization inhibitor, photography, rubber
production, antiseptic, reducing agent, intermediate in
pharmacy, and many others. Hydroxylation reaction
of phenol to produce diphenol had draws many
attentions since 1970s and some catalysts, both
homogeneous and heterogeneous have been applied
in this reaction. Hydroxylation reaction of phenol
becomes environmentally friendly reaction when TS1 (Titanium Silicalite-1) is applied as catalyst and
aqueous H2O2 as oxidant [1]. TS-1 had draws many
attention since last decade because its unique catalytic
characters to selective oxidation reaction of organic
compounds like aromatic hydroxylation, epoxidation
alkenes, ammoximation cyclohexanone and oxidation
of alkene and alcohol with hydrogen peroxide as
oxidant [2]. TS-1 has been commercialize in
hydroxylation reaction of phenol with high
hydroquinone selectivity (hydroquinone/cathecol
ratio = 1) and high H2O2 efficiency [3].
Hydroxylation reaction of phenol with TS-1 catalyst
shows high activity and selectivity, become clean
Proceeding Book
reaction
with
low
H2O2
non-productive
decomposition, and high catalyst stability [4].
TS-1 can lessens tar product and side
products which have potential as pollutant. Reaction
mechanism of phenol hydroxylation is as follows: (1)
TS-1 will decompose H2O2 (oxidation agent) which
has hydrophilic character to form titanium-peroxo
radical (initiation step), then (2) propagation step in
solution [5]. This mechanism can be explained via
titanium-peroxo complex formation mechanism as
intermediate from reaction between H2O2 and TS-1
catalyst [2, 6-9]. The rate of the formation of
titanium-peroxo depended on the rate of H2O2 reach
to active site in TS-1. H2O2 is hydrophilic, that is
quite different from hydrophobic character of TS-1
[10], consequently the reaction rate of phenol
hydroxylation reaction is tends to be low [7]. One of
the way to increase phenol hydroxylation reaction
rate with TS-1 catalyst is by making TS-1 become
more hydrophilic character, and the reaction rate of
phenol hydroxylation will be much faster and shows
increasing of catalytic activity and selectivity higher
than TS-1. Hydrophilic improvement of catalyst can
be carried out by addition of metal oxide which leads
to increasing of acidity properties. The existence of
metal oxide in TS-1 catalyst can gives acid site which
capable to increase catalyst hydrophilicity, so that
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ISBN : 978 979 19201 0 0
reactant adsorption in catalyst becomes faster [11,12].

Heterogeneous catalytic process in phenol
hydroxylation reaction can be carried out with pure
metals oxide or supported oxide such as MoO3,
CuO/SiO2, Fe2O3, Fe2O3/Al2O3, Co3O4, V2O5 and
colloid particle of TiO2. However, this metal oxides
show very low catalytic activity and selectivity [13].
In previous research by Indrayani [14],
synthesis and catalytic activity were carried out with
low-loading of MoO3/TS-1 catalyst in phenol
hydroxylation reaction. MoO3/TS-1 catalysts have
showed improvement of hydrophilicity along with the
increasing of MoO3 content in MoO3/TS-1 catalyst.
The improvement of hydrophilic character of
MoO3/TS-1 catalyst is also accompanied with the
improvement of its catalytic activity in phenol
hydroxylation reaction. In this research, TS-1 catalyst
was modified by addition of metal oxide Fe2O3 on the
surface of TS-1. The existence of Fe2O3 on the TS-1
surface, is expected to bring this new catalyst
(Fe2O3/TS-1) become higher hydrophilic character
compared to TS-1, and the rate of phenol
hydroxylation reaction becomes faster than TS-1.
Experimental
Samples TS-1 were prepared according to a
procedure described earlier by Taramasso et al.
(1983). Tetraethyl orthosilicates, TEOS (Merck,
98%) containing 0.3145 mol of silicon was placed
into a Teflon beaker and vigorously stirred, tetraethyl
orthotitanate, TEOT (Merck, 95%) containing 0.0032
mol of titanium in isopropyl alcohol was carefully
added dropwise into this TEOS. The beaker was
covered with parafilm to avoid hydrolysis. The
temperature of the mixture was raised to 35oC and the
reactants were mixed homogeneously for half an hour
to obtain depolymerisation of the titanate oligomers
that may be present in TEOT. Then the mixture was
cooled to about 0oC. The solution of
tetrapropylammonium hydroxide, TPAOH (Merck,
20% TPAOH in water), which was used as template,
was also cooled to 0oC. After a few minutes, TPAOH
containing 0.1287 mol of TPAOH was added dropwise slowly into the mixture of TEOS and TEOT. At
first, one should wait a few minutes after addition of a
few drops of TPAOH solution before more TPAOH
solution is added, to avoid precipitation. Stirring and
cooling were continued during this process. After the
addition of about 10 mL the addition rate of TPAOH
solution was increased. When the addition of TPAOH
was completed, the mixture was heated in the
temperature range of 80-90oC for about 4 h in order
Proceeding Book
for the hydrolysis of TEOS and TEOT to take place.

Distilled water was added to increase the volume of
the mixture to about 127 mL, after which a clear gel
was obtained. The gel was transferred into a 150 mL
autoclave and heated at 175oC under static condition.
The material was recovered after 4 days of
hydrothermal crystallization by centrifugation and
washing with excess distilled water. A white powder
was obtained after drying in air at 100oC overnight.
Silicalite was synthesized by using the same
procedure without the addition of TEOT. The
calcination of the sample to remove the template was
carried out under static air at 550oC for 5 h with
temperature rate at 1o/min [15].
is
Catalyst
TS-1
and
Fe2O3/TS-1
characterized with X-ray diffraction (XRD)
technique, X-ray powder diffraction (XRD) patterns
were collected using the Ni-filtered Cu-K radiation
( = 1.5406 ), the infrared spectrum is used for IR
absorption spectra analysis with KBr palette method.
The infrared spectrum is recorded from wavenumber
1400400 cm1. Catalysts hydrophilicity is analyzed
by catalyst sample powder dispersion method at water
phase and organic phase mixture (water and xylene).
A mixture of xylene and water, which do not mix
with each other, is employed to test the hydrophobic
characteristics of the samples. Xylene and water of
the same volume are added into a test tube to form a
stable phase interface Unmodified and modified
particles are, respectively, dispersed in the xylene
water system and stirred. After the mixture has
stabilized, the hydrophobic characteristics can be
qualitatively evaluated by inspecting the state of the
floating/sinking of samples at the interface. The
criterion of hydrophobic index is shown in table 2.

Fe2O3/TS-1 catalysts were characterized by
X-ray diffraction technique. The XRD patterns were
showed in Figure 1. Characteristic diffraction lines of
TS-1 is observed at 2 = 7,94; 8; 23.08; 23.62; 23.88;
23.92. The peak at 2 around 24 is observed for the
change of crystal symmetry from monoclinic
symmetry, which is symmetry of silicalite-1, becomes
orthorombic symmetry which is symmetry of TS-1.
This Phenomenon indicates that titanium atom is
already in the framework structure of TS-1 [18]. Xray diffraction pattern of Fe2O3/TS-1 with various of
Fe2O3 loading showed similar pattern with parent TS1 sample. This finding indicated that the MFI
structure of TS-1 is not collapsed after impregnation
of Fe2O3. Therefore, the low content of Fe2O3 (up to
455

January 24, 2009
ISBN : 978 979 19201 0 0
4% wt) on TS-1 catalyst surface doesn't change the
initial
structure
framework
of
TS-1.
Figure 1. X-ray Diffractogram Pattern of TS-1 dan Fe2O3/TS-1

The XRD peak intensity of the samples at 2 around
23.00o is decrease along with the increasing of Fe2O3
loading in TS-1 (table 1). This result indicates that
Fe2O3 were already located on the TS-1 surface.
Table 1. Crystallinity of Fe2O3/TS-1 and TS-1
Intensity at
Samples Code
2 = 23.00o,
Cps
TS-1 (2 = 23.060o)
3288
0,5Fe2O3/TS-1 (2 = 23.167o)
3030
1Fe2O3/TS-1 (2 = 23.183o)
2964
2Fe2O3/TS-1 (2 = 23.138o)
2349
4Fe2O3/TS-1 (2 = 23.302o)
2332
shows absorption band at wavenumber around 1100,

800, and 450 cm-1, which is vibration mode of SiO4 or
AlO4 tetrahedral. Absorption band at wavenumber
around 1100 cm-1 is unsymmetrical vibration mode of
Si-O-Si, and absorption band at wavenumber around
800 cm-1 is its symmetrical vibration mode.
Absorption band at wavenumber around 1230 and
547 cm-1 is characteristic for tetrahedral structure in
framework zeolite MFI [19]. Absorption band at
wavenumber around 970 cm-1 is characteristic of TS1 which is vibration mode of stretching Si-O from
unit [SiO4] which tied at atom Ti4+ with tetrahedral
coordination in TS-1 framework. Absorption band at
this wavenumber is evidence that titanium atom has
already stayed inside the structure of catalyst
framework [20].
Infrared spectra of the samples are shown in

fig 2. Catalyst samples of TS-1 and Fe2O3/TS-1
Proceeding Book
456

January 24, 2009
ISBN : 978 979 19201 0 0
4 Fe2O3/TS-1
2 Fe2O3/TS-1
%T
1 Fe2O3/TS-1
TS1
970 cm-1
1100 cm-1
0.5 Fe2O3/TS-1
1300
1200
1100
1000
900
800
700
600
450 cm-1
547 cm-1
800 cm-1
1230 cm-1
1400
silicalite
500
400
Figure 2. IR Spectra of TS-1 and Fe2O3/TS-1 samples with various loading
wavenumber, cm-1
Proceeding Book
457

January 24, 2009
ISBN : 978 979 19201 0 0
Hydrophilic
Table 2. Hydrophilicity Character Definition [21]

Samples sink into water quickly and completely
Hydrophilic
Hydrophilic
Completely Hydrophobic
Samples sink into water not so quickly, but completely
Samples float at first and then sink into water slowly and completely
Samples float at first and then sink into water slowly. Part of the powder
floats on surface of water and, after agitation, sinks into water
completely
Samples float on the surface of water. After a long time agitation, part of
the powder still floats on the surface of water
Samples float on the surface of water even with strong agitation for a
long time
Table 3. Hydrophobicity Character of TS-1 and Fe2O3/TS-1 Samples

Sample
Index
Character
Water sinks time
(seconds)
TS-1
5
1 : 08.4
0,5Fe2O3/TS-1
1 : 02.4
1Fe2O3/TS-1
0 : 47.2
2Fe2O3/TS-1
0 : 36.9
4Fe2O3/TS-1
0 : 34.1
Catalyst hydrophilicity character analysis is

carried out by catalyst samples dispersion method in
the mixture of water and organic phase (xylene).
The results of hydrophobic tests are shown
in Table 3. All samples seem to show similar
behavior during the hydrophilicity test, this indicates
that the addition of metal oxide on TS-1 surface
didnt give too much effect in TS-1 catalyst
properties, which is partially hydrophobic.
Nevertheless, the addition of metal oxide on TS-1
surface makes Fe2O3/TS-1 catalyst become much
more hydrophilic than TS-1 catalyst. It can be seen in
table 3 that the higher Fe2O3 loading in TS-1 catalyst
resulted in the faster sinks into water. From Table 3,
it can be concluded that there is the increasing of the
catalyst hydrophilicity character along with the
increasing of metal oxide Fe2O3 content at TS-1
catalyst surface.
Proceeding Book
Conclusion
1.
2.
3.
Catalyst TS-1, 0,5Fe2O3/TS-1, 1Fe2O3/TS1, 2Fe2O3/TS-1, and 4Fe2O3/TS-1 has been

successfully synthesized
Catalyst 0,5Fe2O3/TS-1, 1Fe2O3/TS-1,
2Fe2O3/TS-1, and 4Fe2O3/TS-1 still have
orthorombic structure MFI type which is
characteristic of TS-1 catalyst.
Catalyst hydrophilicity character increases
successively from TS-1, 0.5Fe2O3/TS-1,
2Fe2O3/TS-1,
and
1%Fe2O3/TS-1,
4Fe2O3/TS-1.
Acknowledgement
We gratefully acknowledge funding from the
Directorate General of Higher Education, Indonesia,
458

January 24, 2009
ISBN : 978 979 19201 0 0
References
[1] Tang, H., Ren, Y., Yue, B., Yan, S., He, H.
(2006),
Cu-incorporated
Mesoporous
Materials : Synthesis, Characterization and
Catalytic Activity in Phenol Hydroxylation,
Journal of Molecular Catalysis A :
Chemical, Vol. 260, hal. 121-127.
[2] Liu, H., Lu, G., Yanglong Guo, Yun Guo, dan
Wang, J. (2006), Chemical Kinetics of
Hydroxylation of Phenol Catalyzed by TS1/Diatomite
in
Fixed-Bed
Reactor,
Chemical Engineering Journal, Vol. 116,
hal. 179186.
[3] Choi, J., Yoon, S., Jang, S., Ahn, W. (2006),
Phenol Hydroxylation Using Fe-MCM-41
Catalysts, Catalysis Today, Vol. 111, hal.
280-287.
[4] Liu, X., Wang, X., Guo, X., Li, G. (2004), Effect
of Solvent on the Propylene Epoxidation
over TS-1 Catalyst, Catalysis Today, Vol.
93-95, hal. 505-509.
[5] Kurian, M., Sugunan, S. (2006), Wet Peroxide
Oxidation of Phenol Over Mixed Pillared
Montmorillonites, Chemical Engineering
Journal, Vol. 115, hal. 39-146.
[6] Vayssilov, G. N. dan van Santeny, R. A. (1998),
Catalytic Activity of Titanium Silicalites
a DFT Study, Journal of Catalysis, Vol.
175, hal. 170174.
[7] Sun, J., Meng, X., Shi, Y., Wang, R., Feng, S.,
Jiang, D., Xu, R., Xiao (2000), A Novel
Catalyst of CuBiVO Complex in Phenol
Hydroxylation with Hydrogen Peroxide,
Journal of Catalysis, Vol. 193, hal. 199206.
[8] Wilkenhner, U., Langhendries, G., van Laar, F.,
Baron, G. V., Gammon, D. W., Jacobs, P.
A., dan van Steen, E. (2001), Influence of
Pore and Crystalline Titanosilicates on
Phenol
Hydroxylation
in
Different
Solvents, Journal of Catalysis, Vol. 203,
hal. 201-212.
[9] Bonino, F., Damin, A., Ricchiardi, G., Ricci, M.,
Spano`, G., DAloisio, R., Zecchina, A.,
Lamberti, C., Prestipino, C., dan Bordiga, S.
(2004), Ti-Peroxo Species in The TS1/H2O2/H2O System, Journal of Physical
Chemistry B, Vol. 108, hal. 3573-3583.
[10] Armaroli, T., Bevilacqua, M., Trombetta, M.,
Milella, F., Alejandre, A. G., Ramirez, J.,
Notari, B., Willey, R. J., dan Busca, G.
(2001), A Study of The External and
Internal Sites of MFI-Type Zeolitic
Materials through The FTIR Investigation of
Proceeding Book
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
The Adsorption of Nitriles, Applied

Catalysis A : General, Vol. 216, hal. 5971.
Nur, H., Prasetyoko, D., Ramli, Z., Endud, S.
(2004), Sulfation: A simple Method to
enhance the Catalytic Activity of TS-1 in
Epoxidation of 1-octene with Aqueous
Hydrogen
Peroxide,
Catalysis
Communications . Vol.5, hal. 725728.
Prasetyoko, D., Ramli, Z., Endud, S., Nur, H.
(2005), Enhancement of Catalytic Activity
of
Titanosilicalite-1Sulfated
Zirconia
Combination Towards Epoxidation of 1Octene With Aqueous Hydrogen Peroxide,
Reaction Kinetics Catalysis Letter, Vol. 86,
hal. 83-89.
Ray, S., Mapolie, S. F., Darkwa, J. (2007),
Catalytic Hydroxylation of Phenol using
Immobilized
Late
Transition
Metal
Salicylaldimine Complexes, Journal of
Molecular Catalysis A : Chemical, Vol. 267,
hal. 143-148.
Indrayani Suci, (2008), Aktivitas Katalitik
MoO3/TS-1 pada Reaksi Hidroksilasi Fenol
menggunakan H2O2, Tesis M.Si, Jurusan
Kimia FMIPA Institut Teknologi Sepuluh
Nopember, Surabaya.
Taramasso, M., Perego, G. and Notari, B.
(1983), Preparation of Porous Crystalline
Synthetic Material Comprised of Silicon and
Titanium Oxides. (U. S. Patents No.
4,410,501).
Choudhary, V. R., Jana, S. K., Mamman, A. S.
(2002), Benzylation of Benzene by Benzyl
Chloride over Fe-modified ZSM-5 and H-
Zeolites and Fe2O3 or FeCl3 deposited on
Micro-,
Meso-,
and
Macro-porous
Supports, Microporous and Mesoporous
Materials, Vol. 56, hal. 65-71.
Hattori, H., Ogawa, T., Jones, F., Knudson, C.,
Willson, W., Rindt, J., Mitchell, M.,
Stenberg, V., Radonovich, L., Janikowski, S.
(1985), Reduction Activities of Fe2O3/SiO2
Catalysts with Hydrogen Sulphide and
Hydrogen, Fuel, Vol. 65, hal. 780-785.
Li, Y.G., Lee, Y.M., Porter, J.F. (2002), The
Synthesis and Caracterization of Titanium
Silicalite-1, Kluwer Academic Publishers,
hal. 0022-2461.
Drago, R. S., Dias, S. C., McGilvray, J. M.,
Mateus, A. L. M. L. (1998), Acidity and
Hydrophobicity of TS-1, Journal of
Physical Chemistry, Vol. 102, hal. 15081514.
459

January 24, 2009
ISBN : 978 979 19201 0 0
[20] Li, G., Wang, X., Guo, X.,Liu, S., Zhao, Q., Bao,
X., Lin, L. (2001), Titanium Species in
Titanium Silicalite TS-1 Prepared By
Hydrothermal
Method,
Materials
Chemistry and Physics, Vol. 71, hal. 195201.
Organic Modification of Ultrafine Particles
using Carbon-dioxide as the Solvent,
Journal of Powder Technology, Vol. 139,
hal. 148-155.
Proceeding Book
460

January 24, 2009
ISBN : 978 979 19201 0 0
New Mixed Ligands Complexes of Zinc(II), Cadmium(II) and Bismuth(III)

With Dithiocarbamates and 2,2-Bipyridyl
Normah Awang1, Ibrahim Baba2 and Bohari Mohd Yamin2
1
Environmental Health Programme, Faculty of Allied Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja
Muda Abdul Aziz, 50300 Kuala Lumpur
normahawang1969@yahoo.com
+60326878034
2
School of Chemical Sciences and Food Technology, Faculty Science and Technology, Universiti Kebangsaan
Malaysia, 43600 Bangi, Selangor
Abstract
A new series of zinc(II), cadmium(II) and bismuth(III) complexes with mixed ligands, dithiocarbamate and 2,2bipyridyl were successfully synthesized using in situ method. Microelemental analysis data of the complexes are
in agreement with the general formula, M[S2CNRR]nbipy (M = Zn, Cd & Bi; R = s-butyl, R = propyl; R =
N)
benzyl, i-propyl; bipy = 2,2-bipyridyl). Infrared spectra of the complexes showed that the thioureide (C
-1
-1
band is in the regions 1438 1453 cm . The unsplitting band of (C-S) in the region 930 1000 cm indicates the
13
bidentate nature of the chelated dithiocarbamate ligands. The C NMR chemical shift of the carbon atom of the NCS2 group appeared in the range of 201.67 208.27 ppm. The crystal structure of zinc(II)
benzylisopropyldithiocarbamate(2,2-bipyridyl) supports the elemental and spectroscopic data in which two
dithiocarbamates and one bipy ligands chelated to the central Zn atom in bidentate manner in a distorted
octahedron environment.
Keywords: dithiocarbamate; chloroform; IR spectra; biological activity
Introduction
For several years considerable attention has been paid
to dithiocarbamate compounds. Firstly, their
biological effects have been researched, including
antialkylation, anti-HIV properties [1] and antitumor
activity against leucemic cells [2]. Some
dithiocarbamate complexes also have some practical
applications. For example, they are used in
agriculture as fungiside and pesticide [3].
The 1:1 adducts of zinc and cadmium
dialkyldithiocarbamates with 2,2-bipyridyl have
been reported and some of these complexes are very
active accelerators for the vulcanization of rubber and
low temperature vulcanization of latex [4]. The
crystal structure of Zn[S2CN(C2H5)2]2(2,2-bipy) has
been reported [5].
In spite of the fact that many
dithiocarbamate compounds with different transition
metals are described in the chemical literature, we
have only considered Zn(II), Cd(II) and Bi(III)
coordination compounds with non-symmetrical
dithiocarbamates with the general formula
Proceeding Book
M[S2CNRR]nbipy. (M = Zn, Cd & Bi; R = s-butyl,

R = propyl; R = benzyl, Ri-propyl; bipy = 2,2bipyridyl). So far, no information on complexes of
this
type
with
the
sec-butylpropyl
and
benzylisopropyldithiocarbamate ligands were found
in the literature.

Reagents
All the reagents and solvents employed were
commercially available analytical grade materials and
were used as supplied, without further purification. Nbenzylisopropylamine, 2,2-bipyridyl and ethanol
(95%) were obtained from Fluka Chemicals. Carbon
disulphide and methanol (99.5%) from Ajax
Chemical Ltd. Bismuth(III) chloride was obtained
from Hayashi Pure Chemical Indsutries Ltd.
Cadmium(II) dichloride monohydrate, chloroform
and zinc(II) chloride were purchased from Merck.
Physical and spectroscopic measurement
461

January 24, 2009
ISBN : 978 979 19201 0 0
Elemental analyses were performed on a Fision EA

1108 CHN Elemental Analyser. Melting points were
1
days, the crystals separated out and washed with cold

ethanol.
determind on a Electrothermal IA 9100 apparatus. H
Results And Discussion
and C NMR spectra were recorded in CDCl3

solution on a Joel JNM LA400 spectrometer with
chemical shifts relative to tetrametylsilane. IR spectra
were obtained as KBr pellets on a Perkin Elmer
FTIR Model GX spectrophotometer in the frequency
The Mn+[S2CNRR]m(bipy) complexes (n = 2, m = 2;

n = 3, m = 3; R = s-C4H9, R = CH3; R = C7H7, iC3H7; bipy = 2,2-bipyridyl) were prepared via a
straightforward process involving only two steps. All
the compounds were non-hgroscopic and stable in air.
They were insoluble or sparingly soluble in most
common organic solvents and very soluble in
chloroform. The results of elemental analyses (Table
1) are in good agreement with those required by the
proposed formulae. The formation of these complexes
may proceed according to the following equation
given below.
13
-1
-1
-1
range 4000 500 cm and 500 cm - 200 cm
Synthesis of dithiocarbamate complexes

The mixed-ligand complexes were prepared by
adding equimolar of metal dithiocarbamate
compound (zinc(II), cadmium(II) and bismuth(III))
and 2,2-bipyridyl in the mixture of ethanol and
chloroform solutions. The method used to prepare the
metal dithiocarbamate compounds were synthesized
by a method reported earlier [6]. The resulting
mixture was stirred for one hour and the solvent was
allowed to evaporate at room temperature. After two
M[S2CNRR]n + C10H8N2
M[S2CNRR]n(C10H8N2)
M = Bi(III), Cd(II), Zn(II); n = 2 or 3; R = C7H7, R
= i-C3H7; R = s-C4H9, R = C3H7
Table 1. Physical and elemental analysis data of mixed-ligand complexes

Compound
Zn[S2CN(C7H7)(iC3H7)]2bipy
(compound 1)
Cd[S2CN(C7H7)(iC3H7)]2bipy
(compound 2)
Zn[S2CN(sC4H9)(C3H7)]2bipy
(compound 3)
Cd[S2CN(sC4H9)(C3H7)]2bipy
(compound 4)
Bi[S2CN(sC4H9)(C3H7)]3bipy
(compound 5)
Colour
Yellow
Yellow
Yellow
Yellow
Orange
Melting
point
(C)
165.9166.5
223.2224.4
133.8134.3
194.8195.3
115.8116.5
The infrared spectra of the title compounds

and important characteristic absorption bands, along
with their proposed assignments are summarized in
Table 2. The IR spectra of the compounds are very
similat to each other, except some slight shifts and
intensity change of a few vibration bands caused by
different metal ions, which indicate that the
compounds have similar structures. Coordination in
the mixed-ligand mainly affected the C-N and C-S
stretching bands [7].
Proceeding Book
% Found (calcd)
N
S
55.80
(57.37)
52.30
(53.60)
52.83
(51.88)
47.68
(48.12)
43.84
(43.64)
5.03
(5.38)
4.65
(5.02)
7.27
(6.65)
6.65
(6.17)
6.76
(5.99)
8.36
(8.37)
7.51
(7.82)
9.55
(9.31)
9.71
(8.64)
8.57
(7.49)
20.23
(19.12)
17.34
(17.87)
22.18
(21.28)
19.09
(19.74)
21.80
(20.54)
M
11.32
(9.77)
14.07
(15.69)
8.73
(10.87)
16.00
(17.33)
20.87
(22.35)
Table 2. The important infrared absorption bands of

compound 1-5 (cm-1)
Compound (C
N) (N- (C
S) (M-
1
2
3
4
5
1440
1438
1441
1439
1453
1174
1171
1196
1194
1189
967
970
967
957
951
386
387
376
386
358
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January 24, 2009
ISBN : 978 979 19201 0 0
The selected 1H NMR peaks for compounds

1-5 are showned in Table 3. The aromatic proton
signals for 2,2-bipyridyl in compounds 1-5 were
observed in the range 7.33 9.01 ppm. This signal
was not observed in the 1H NMR spectra for metal
dithiocarbamate compounds. Two proton signals
from 2,2-bipyridyl in compounds 1-4 have shifted
which one signal to downfield and the other one

signal to upfield. These shifts indicate that 2,2bipyridyl has been coordinated to the metal atom. The
IR spectra data combined with these data showed that
the 2,2-bipyridyl has coordinated to the metal atom
in
all
of
these
compounds.
Table 3. The selected 1H and 13C NMR data (, ppm) for compounds 1-5
Compound
Formula
2,2-bipyridyl (C10H8N2)
Zn[S2CN(C7H7)(iC3H7)]2bipy
Cd[S2CN(C7H7)(iC3H7)]2bipy
Zn[S2CN(sC4H9)(C3H7)]2bipy
Cd[S2CN(sC4H9)(C3H7)]2bipy
Bi[S2CN(sC4H9)(C3H7)]3bipy
The most important signal in the 13C NMR

spectra was the chemical shift for N13CS2 carbon. The
N13CS2 chemical shifts for compounds 1-5 were
observed in the range 201.67-208.27 ppm which not
observed in the 13C NMR spectra for 2,2-bipyridyl
compund. The N13CS2 chemical shift for compounds
1 and 2 dropped slightly to downfield compared to
the parent compounds (205.08 and 205.77 ppm
respectively). The high values of N13CS2 chemical
shifts could be explainded by an increase of bond
order in the whole NCS2 moiety [8] which means that
the chelation of 2,2-bipyridyl to the metal atoms has
promoted the delocalization of the unshared electron
pair in the nitrogen atoms in the dithiocarbamate
groups.
Suitable crystal for X-ray crystallographic
studies of compound 2 were obtained by slow
evaporation of a chloroform:ethanol mixture at room
temperature. The dithiocarbamate ligands and 2,2bipyridyl are bidentically chelated to the zinc atom
and the coordination geometry around zinc was
distorted octahedral.
Conclusion
The elemental, spectroscopic and crystallographic
data showed that the new mixed-ligand complexes
have
been
successfully
synthesized.
The
Proceeding Book
H NMR
(bipy)
8.70 (d), 8.41 (d), 7.83 (t),
7.33 (t)
8.95 (d), 8.26 (d), 7.86 (t),
7.33 (t)
9.01 (d), 8.19 (d), 7.95 (t),
7.48(t)
8.82 (d), 8.35 (d), 7.85 (t),
7.35 (t)
8.95 (d), 8.26 (d), 7.86 (t),
7.33 (t)
8.70 (d), 8.40 (d), 7.84 (t),
7.33 (t)
13
C NMR
(N13CS2)
206.62
208.27
203.88
205.93
201.67
dithiocarbamate ligands and 2,2-bipyridyl were

chelated to the metal atom to form the
hexacoordinated mixed-ligand complexes. The
crystallographic study of compound 2 showed that
both of the dithocarbamate ligands and 2,2-bipyridyl
were bidentically chelated to the zinc atom.
Acknowledgement
The authors gratefully acknowledge the research
grant provided by The Malaysian Government (IRPA
09-02-02-0048-EA144) and Universiti Kebangsaan
Malaysia for financial support. Technical support
from laboratory assistants of Faculty Science and
Technology, Universiti Kebangsaan Malaysia is
gratefully acknowledged.
References
[1] Hersh, E.M., Brewton,G., Abrams,D., Bartlett,J.,
Galpin,J., Gill,P., Gorter,R., Gottlieb,M.,
Jonikas,J.J.,
Landesman,S.,
Levine,A.,
Marcel,A.,
Petersen,E.A.,
Whiteside,M.,
Zahradnik,J., Negron,C., Boutitie,F., Caraux,J.,
Dupuy,J. & Salmi,R. 1991. Ditiocarb sodium
(diethyldithiocarbamate) therapy in patients with
symptomatic HIV infection and AIDS: A
463

January 24, 2009
ISBN : 978 979 19201 0 0
randomized, double-blind, placebo-controled,

multicenter study. J. Am. Med. Assoc.,
265:15381544.
[2] Mital, R., Jain, N. & Srivastava, T.S. 1989.
Synthesis, characterization and cytotoxic studies
of diamine and diimine palladium(II) complexes
of diethyldithiocarbamate and binding of these
and analogous platinum(II) complexes with
DNA. Inorganica Chimica Acta, 166(1):135-140.
[3] Montgomery, J.H. 1993. Agrochemical Desk
Reference Environmental Data, Lewis Publisher,
Michigan.
[4] Bateman, L. 1963. The chemistry and physics of
rubber like substance, Maclaren, London.
[5] Zemskova, S. M., Glinskaya, L. A., Durasov, V.
B., Klevtsova, R. F. & Larionov, S. V. 1994.
Mixed-ligand complexes of zinc(II) and
cadmium(II) diethyldithiocarbamates with 2, 2-
Proceeding Book
bipyridyl and 4, 4-bipyridyl: synthesis, structure

and thermal properties. J. Struct. Chem. 34: 794802.
[6] Awang, N., Baba, I. & Yamin, B.M. 2004.
Synthesis and characterization of secbutylpropyldithiocarbamate compounds: crystal
structures of Zn(s-BuPrDtc)2 and
Cd(sBuPrDTC)2. AJSTD 21(4):309-318.
[7] Airoldi, C. & Oliveira, S. F. D. 1990. Adducts of
cadmium diethyldithiocarbamate with bidentate
nitrogen ligands. Inorg. Chim. Acta 174: 103108.
[8] Nomura, R., Fujii, S., Takabe, A. & Matsuda, H.
1989. Preparation of novel metal dithiocarbamate
complexes containing -OH group. Stabilization
effect of the OH group on the HNCS-Mt linkage.
Polyhedron 8(15): 1891-1896.
464

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ISBN : 978 979 19201 0 0
Titanium Dioxide Thin Film as Solar Photocatalyst for A Chlorinated

Degradation of Organics Contaminate
Muneer. M.Baabbad1,Abdul Amir H.Kadhum1,Abu Bakar Mohamad 1,
Mohd S.Takriff 1,Kamaruzzaman. Sopian2.
1
Faculty of Engineering and Built Engineering, Universiti Kebangsaan Malaysia

43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia.
2
Solar Energy Research Institute (SERI) Universiti Kebangsaan Malaysia
43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia.
Abstract
This paper is reviewing a Titanium dioxide thin film used in solar photocatalytic process. Solar photocatalytic
technology is one of the major applications in the degradation of organic pollutants in water. The
heterogeneous photocatalytic distractions of organic contaminates on thin film fixed bed reactor (TFFBR) is
investigated. The degradation is studied using TiO2 and also with different doped such as Pd and Fe3+
photocatalysts under solar light illumination. The thin films were prepared with the dip-coating technique
(Sol-Gel) using titanium tetra-iospropoxide as a raw material for synthesis of thin film, followed by thermal
treatment at 400Co. The sample characterized by X-ray diffraction, UV-vis spectroscopy, scanning electron
microscopy and atomic force microscopy. The photoactivity of various films were tested using different
organic pollutants such as phenol and 4-chlorophenol (one of the most common water pollutants).The
photoeffcinency obtained is approximately similar to that obtained using suspension. This was done for
avoiding many operational complications such as separation of the catalyst and continuous of process.
Keywords: Titanium dioxide thin film (TiO2), solar photocatalysis, organics contaminates.
Introduction
Photocatalysis is the generally accepted term for a
process in which light and a catalyst bring about or
accelerate a chemical reaction. The IUPAC
definition states photocatalysis as a catalytic
reaction involving light absorption by a catalyst or
by a substrate. In semiconducting photocatalysis,
no energy is stored; instead there is an acceleration
of a reaction by a photon-assisted process. Titanium
dioxide has been the practical photocatalyst [1] of
choice for a variety of reactions due to its high
stability and oxidising power. It functions by
absorbing sub band-gap radiation, this generates an
electron and positive hole that can migrate to the
surface of the titania and promote oxidation and
reduction reactions. Powders and thin films of
titania will photodegrade a wide range of organic
chemicals in water [2-3]. During the last decades
several efforts have been focused on improving
decontamination of water [4] one of the most
attractive options is the treatment by oxidation
using a semiconductor, typically titanium dioxide,
in combination with solar irradiation. This process
can destroy organic matter, transforming organic
carbon to CO2 and H2O employing just solar energy
and a low cost non-toxic catalyst.
Thin films of TiO2 on glass can be doing by a
number of different methods. It has been often
prepared by expensive methods as pulsed laser
Proceeding Book
deposition [5], reactive evaporation [6] and

chemical vapour deposition [7-9]. The simplest and
Low cost preparation methods are the sol-gel
processes [10-14] including dip or spin-coating [14]
as the final step of preparation. The latter, along
with the source of titania, also determines the grain
size, structure, phase and density of sol-gel derived
films [15-17]. Although titania thin-films have been
proven to be effective in photo-oxidising organic
substances, they can only do so under sub
approximately 350 nm radiation. Its band-gap of
3.2 eV means that titania can use less than
approximately 1% of the solar spectrum. Gerischer
and Heller [18] have proposed that the activity of a
photocatalyst is limited by the rate of electron
transfer to oxygen on the surface of the catalyst.
There has been some research that suggests the
modification of the TiO2 surface by Noble metals
increases the efficiency of electron transfer to
oxygen, which in turn increases the photooxidation
efficiency. Some metals such as Pd and Fe+3 have
also been doped into titania in order to improve its
physical and optical properties.

Sol-Gel synthesis process
The TiO2 film was prepared using water; alcohol as
solvent and different salts of metal oxide. In this
465

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ISBN : 978 979 19201 0 0
case, used titanium tetra-isopropoxide (TTIP) as a

titanium dioxide precursor became easily TiO2 type
due to rapid hydrolysis, and then, the acquired final
products were divided in two parts, powder and
solution, which are necessary as centrifugation for
the separation of these to get a colloidal solution for
TiO2 film [19] and procedure indicated in Fig 1 (a)
[20] .An aqueous solution molar ratio different
according of the type material films, show in the
Table 1.
Characterization of TiO2 films using the solgel

process
The use of solgel multistep process led to the
production of transparent nanocrystalline TiO2 thin
films with excellent reproducibility, scratch
resistance and adherence on the glass substrates.
Also the low cost one technique produced opaque
and thicker films with good uniformity, and with
properties closely related to the starting powder
material. [23]. Right now, the research for
improving the photocatalytic activity of TiO2
mainly focus on the aspects as follows: doping of
metal ions, surface depositing of noble metal,
recombination
of
semiconductor,
surface
photosensitization and so on. Doping of metal ions
has been largely employed with the aim to enhance
the photocatalytic activity of TiO2 [24].Scanning
electron microscopy was employed to perform at
first the surface characterization of the
manufactured films. Crystallinity of the TiO2 thin
film was anatase determined by X-ray diffraction
(XRD) using a diffract-meter with Cu K radiation,
consisted with the literature [25]. The transmittance
and absorbency of thin film were measured by UV
visible spectrophotometer.
Dip-coating
The glass substrates were dipped in the solution by
a locally constructed clipping machine. The
withdrawal rate used for the single coated films was
different speed show in the Table 1 .After each
coat, the film was allowed to dry at room
temperature for 10 min. The procedure was
repeated to obtain multiple coatings, Samples were
annealed in a furnace at 400-500 Co for 1-3 h in air
to fully decompose the precursor and obtain
crystalline samples. The rate of heating and cooling
was 5 Co/ min [21-22].
TTIP
Alchol
H2O
(a)
Acid
(b)
Mixing and Stirring

Titania Sol
Dip Coating
Drying
Baking
TiO2 Thin Film
Figure 1: (a) preparation of TiO2 film by sol-gel, (b) Stages of the dip coating process.
Proceeding Book
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Degradation of pollutants (4- chlorophenols as

example )
The photodegradation of chlorophenols in aqueous
solution has received considerable attention
because these compounds are important xenobiotic
micropollutants of the aquatic environment
originating, for example, from industrial chemical
synthesis. More specifically, 4-chlorophenol (4-CP)
is used for the production of quinizarin (a dye),
clofibrate (a drug), chlorphenesin and dichlorophen
(fungicides) [26]. Therefore, several investigations
of
the
photocatalytic
decomposition
of
chlorophenols using metal oxide semiconductors
either in aqueous heterogeneous suspensions [2731] or in an immobilized form [32-34] have been
published. The kinetics of the photocatalytic 4-CP
The generation of the observed reaction

intermediates can be readily explained though
reaction schemes which involve OH. radical attack
of 4-CP, initially to give the 4-chlorodihydroxycyclodienyl radical, leading on to the
generation of 4-CC, HQ and BQ as intermediates to
the eventual mineralisation of 4-CP. The primary
oxidant appears to be surface absorbed OH radicals
generated through the reaction between a
degradation have commonly been interpreted as

being indicative of a LangmuirHinshelwood- type
mechanism in which the limitation of the 4-CP
decomposition
rate
at
higher
pollutant
concentrations is related to the extent of adsorption
of the pollutant molecule on the TiO2 surface
[30,35]. However, Cunningham et al. showed [31]
that the observed adsorption constants of
chlorophenols on TiO2 in the dark differ from
equivalent data obtained from the kinetic analysis
of their photocatalytic degradation employing the
same TiO2 particles under UVirradiation.
The photo-oxidative mineralisation of 4chloropheno 4-CP) by oxygen and sensitised by
TiO2, can be summarised as follows [36]:
photogenerated valence-band hole and a surfacebound OH- or H2O group. Other sources of oxidant,
which may also make a significant contribution,
include OH. radicals derived from the oxygen
reduction side of the photomineralisation process
and direct attack of the substrate by the
photogenerated hole [37]. Fig. 2 illustrates a typical
degradation reaction scheme for Degussa P25 TiO2
power dispersions in acidic solution.
Figure.2. Reaction scheme illustrating the likely mechanistic pathways to the formation of the major
intermediates, 4-chlorocatechol (4-CC), hydroquinone (HQ) and benzoquinone (BQ), generated during
the photomineralisation of 4-CP.

Proceeding Book
Synthesis -TiO2 films
467

January 24, 2009
ISBN : 978 979 19201 0 0
The films were formed on the glass substrate by

dipping into the aged sol and then with- drawing at
a constant rate to obtain a uniform coating. The
solution remained clear with no white TiO2 microparticles precipitating out. Hydrochloric acid acts as
a catalyst to complete the hydrolysis. The probable
mechanism for the process is shown in Scheme 1.
The titanium alkoxide is protonated in a rapid first
step. This makes the Ti atom more electro- philic
and susceptible to attack form the water [39].
Withdraw of the glass-slide from the fluid-sol
produces a transparent film due to the evaporation

of the solvent and hydrolysis of [Ti-(Oi Pr)4].
During dipping, aggregation, gelation and drying
occurs in seconds to minutes, rather than days as in
bulk sol-gel systems [40]. Annealing of the film
removed any remaining solvent and the structure is
stiffened i.e. a Ti-O-Ti network formed by removal
of the alkoxy and hydroxyl groups to produce an
anatase thin film. It was noted that the most
photocatalyically active films were formed by dipcoating 24 h after the initial hydrolysis.
Scheme 1: illustrate the steps of Synthesis -TiO2 film
Mechanism of degradation process on thin film

The photocatalytic oxidation driven by a large band
gap semiconductor starts with the promotion of
electrons from the valence to the conduction band,
creating an electron-hole couple. The electrons are
removed by reaction with oxygen dissolved in
water and the cationic holes react either with OHand/or H2O adsorbed at the semiconductor surface
to form OH. radicals. Greater amounts of adsorbed
OH- and/or H2O generate a concomitant increase in
the amount of hydroxyl radicals favoring thus the
photodegradation process. Taking into account the
heterogeneous photocatalytic mechanism of a thin
film TiO2 catalyst, the following steps typically
take place [38]: (i) light absorption on the
photocatalytic surface (ii) chemical transformation
of the molecule while several reaction surface sites
are visited (iii) desorption to the liquid phase.
Degradation
contaminate
of
chlorinated
of
resistance and adherence on the glass substrates.

The photocatalytic activities of all of the films were
determined by photodegradation of thin dip-coated
film of chlorinated of organics contaminates. The
most outstanding feature with dip-cotaing method
is that photocatalytic activity is higher when glass
is used as support. Some typical results are reported
in the Table 1.
organics
The use of solgel multistep process led to the

production of transparent nanocrystalline TiO2 thin
films with excellent reproducibility, scratch
Proceeding Book
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ISBN : 978 979 19201 0 0
Table 1 Illustrate Material of Sol-Gel method and Degradation of some Chlorinated Organics contaminate photocatalytic degradation of the 4-chlorophenol concentration as a
function of exposure time to the solar irradiation and using TiO2 thin films as catalysts
No Type of
Ref
TTIP*
Catalyst
Solvent
H2O
Acid
Film
DipOrganic
Time of
Organic
C/C0
Thin
%
.
Mol
Mol
Mol
Mol
Mol
thickne coating
degradation
degradation
degradation
Film
ss
speed
min
%
nm
cm/min
1
TiO2
0.1
0.4
0.1
Hcl
600
10
4-chlorophenol
180
24
41
0.008
2
TiO2
titanium
innsulfonicacid
5002
3,5-dichlorophenol 1600
100
42
butoxide
butanol
600
1.72gm
Fe+3/
TiO2
Pd/ TiO2
5-
TiO2
1
1
0.1
Proceeding Book
Fecl
1
Pd
(NO3)2
0.15
EtOH
20
ethyl
alcohol
7.6
isopropyl
alcohol
0.4
20
0.1
acetic acid 4,
HNO3
0.5
HCl
490
6.9
Dichloroacetic acid
150
80
43
180
2.4
Phenol
1440
83
44
10001600
1,1_-dimethyl4,4_-bipyidium
dichloride
900
95
46
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After 3 h of concentrated solar irradiation, the final

dissolved concentration of 4-chlorophenol is 24%
of its initial for the TiO2 immobilized catalysts. This
means that TiO2 immobilized catalysts high
photoefficiency [41]. A.Mills & J.Wang [36]
reported the temporal variations in: [4-CP], [4-CC],
[HQ], [CO2] and it appears likely that the reaction
scheme illustrated in Fig. 3 is also applicable to
TiO2 films of Degussa P25, that is, there is no
major difference in the overall degradation reaction
mechanism for films or dispersions of the same
TiO2 source material (Degussa P25 in this case).
Photocatalytic experiments took place to evaluate
the films as a possible material for 3,5dichlorophenol (3,5-DCP) pollutant purification
from water. Each experiment included complete
decomposition (100%) of the b 3, 5-DCP but at
long time due to films are endowed with a higher
real surface extension, which readily favors the
photodecomposition process .In fact, such a surface
not only permits the adsorption of a greater number
of pollutant molecules, but also creates a rough
environment where multiple light reflection can
occur, thus considerable increasing the amount of
the adsorbed photons [42] .The titania films
functionalized with iron cations used model of
Dichloroacetic acid (DCA) degradation. Fe/TiO2
film in presence of DCA and oxygen lead to proton
release due to degradation of the organic molecules
[43]. The Fe/Ti films are more effective
photocatalysts with single coated and it give
degradation efficiency 80 %. The photodegradation
of phenol using the film modified with palladium
was superior to that achieved with the pure titanium
film [44]. However, in the case of a film, the
particles are attached to the surface of a solid
substrate, without the occurrence of aggregates, as
in the case of a suspension. Probably, in the case of
thin films, the substratecatalyst repulsion due to
the dissociation of the OH groups present on the
titania surface is negligible, considering that the
catalyst mass is small. Thus, the dominant factor in
the photocatalytic process involving thin films is
mass transport [45]. The photodegradations of 1,1dimethyl-4,4-bipyidium dichloride (Paraquat) with
coating time are compared. First, in case of the film
attained from the solgel method the Paraquat
decomposition slowly increased with an increase of
coating time. In particular, the conversion of
Paraquat was above 90% with four-time coating
after 25 h[46].
commercial titanium tetra-isopropoxide (TTIP).

The results showed that the films possessed good
photocatalytic activity for the degradation of
organics contaminate as a typical photocatalytic
reaction in liquidsolid systems. The modified
films (Pd and Fe3+/ TiO2) prepared by the solgel
route and deposited in film form on the surface of
glass exhibited high photocatalytic activity and also
TiO2 film. Since the use of the fixed catalyst avoids
many operational complications for separation of
the powder catalyst, this represents a great
advantage towards the application of this
technology.
Acknowledgements
The authors greatly a acknowledge to Solar Energy
Research Institute (SERI) Universiti Kebangsaan
Malaysia for its financial support (UKM-RS-02FRGS0004-20007).
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The use of a solgel multistep process allowed
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Proceeding Book
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sensitized removal, photon flux and levels of

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photodegradation of 4-chlorophenol in
water.J. Photochem. Photobiol. A 58: 99
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[36] Mills,
A.
&
Wang,
J.1998.Photomineralisation
of
4chlorophenol sensitised by TiO2 thin films. J.
of Photochemistry and Photobiology A:
Chemistry 118: 53-63.
[37] Hoffmann, M.R., Martin, S.T., Choi, W.&
Bahnemann,
D.W.1995.Environmental
Applications
of
Semiconductor
Photocatalysis, Chem. Rev. 95:69-96.
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Ryabchuk,
V.2000.Turnovers
and
photocatalysis: A mathematical description,
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[39] Sopyan, I., Watanabe, M., Murasawa, S.,
Hushimoto, K., Fujishima, A. 1996. Efficient
TiO2 Powder and Film Photocatalysts with
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Rutile Crystal Structure,Chem. Lett. 25: 6971.

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and Chemistry of Sol-Gel Processing,
Academic Press, New York.
Gelover, S., Mondragn, P., Jimnez,
A.2004. Titanium dioxide sol-gel deposited
over glass and its applicationas a
photocatalyst for water decontamination.
A: Chemistry 165 (2004) 241246.
Arabatzis,
I.M.,
Antonaraki,
S.,
Stergiopoulos,
T.,
Hiskia,
A.,
Papaconstantinou E. , Bernard, M.C.,
Falaras,
P.
2002.Preparation,
characterization
and
photocatalytic
activity
of
nanocrystallinethin film TiO2 catalysts
towards 3,5-dichlorophenol. Journal of
Chemistry 149: 237245.
Smirnova, N., Eremenko, A. & Rusina,
O.2001.Synthesis and characterization of
photocatalytic porous Fe+3/TiO2 Layers on
glass. Journal Sol-Gel Science and
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Cristante, V.M. , Jorge, S. M.A. , Valente,
J. P.S., Saeki, M. J., Florentino, A.O.,
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P.
M.
2007.TiO2
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Applied Catalysis B: Environmental 37:187
196.
472

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Biological Activity of New Schiff Bases Derived From Thiophene and Their
Transition Metal Complexes
Md. Uwaisulqarni Osman1*, M. Ibrahim M. Tahir2, Karen A. Crouse2, A.M. Ali3
1
Department of Chemical Sciences, Faculty of Science and Techology, Universiti Malaysia Terengganu, 21030
Kuala Terengganu, Terengganu Darul Iman, Malaysia.
2
Department of Chemistry, Faculty of Science,Universiti Putra Malaysia,
43400 UPM Serdang, Malaysia
3
Laboratory of Molecular and Cell Biology, Institute of Bioscience, Universiti Putra Malaysia, 43400 Serdang,
Selangor, Malaysia
*uwais@umt.edu.my
Abstract
A new Schiff base formed from S-benzyldithiocarbazate (SBDTC) with selected aldehyde containing a
thiophene ring namely, thiophene-2-carbaldehyde (NS) in 95 % of ethanol have been synthesized.
Complexes of Cobalt(III), Nickel(II), Copper(II), Zinc(II) and Cadmium(II) with this Schiff base was
prepared. The Schiff base and their metal complexes were evaluated for their cytotoxic and
antimicrobial activities. Cytotoxic screening was carried out against Human ovarian cancer cells
(CaOV-3), Human breast carcinoma cells with negative estrogen receptor (MDA-MB-231) and Human
liver carcinoma cells (HEP-G2). Antimicrobial screening was carried out against four bacteria and three
fungi.
Keywords: Schiff Base, metal complexes, S-benzyldithiocarbazate (SBDTC), Cytotoxic, Antimicrobial,
thiophene-2-carbaldehyde
Introduction
Many researchers had been carried on Schiff
bases and their complexes [1, 2, 3, 4, 5] where, Schiff
bases are compounds with structure of C=N(azomethine group) which can be synthesized
through condensation reaction between primary
amines and active carbonyl groups. Usually,
bidentate Schiff base can coordinate with various
transition metals through C=N- (azomethine group)
and C=S (mercaptide group) [6] and gives solid
metal complexes together with various geometry
depends on the nature of the metals. Their flexibility
in chelating with transition metals had emerged the
knowledge on relationship between coordination
chemistry and their interesting and important
properties e.g antimicrobial, antifungal and
anticancer [6,7, 8, 9, 10].
The present study was under taken to
investigate more on biological activity of the Schiff
base derived from the S-benzyldithiocarbazate
(SBDTC) with thiophene-2-carbaldehyde (NS).
However, all physico-chemical analyses to confirm
the structures had been done using IR, magnetic, 1H
Proceeding Book
and 12C NMR measurements, thermogravimetric

analysis, CHNS analyses and X-Ray Crystallography.
Furthermore, all the results are not included in the
present study.

Cytotoxic Assay
All the Schiff base and metal complexes were tested
to determine their cytotoxicity against CaOV-3
(Human Ovarian Cancer cells), MDA-MB-231
(Human breast carcinoma cells with negative
estrogen receptor) and HEP-G2 (Human Liver
carcinoma cells) cell lines at Faculty of Medicine and
Health Science, Universiti Putra Malaysia. The cell
lines were obtained from the National Cancer
Institute, U.S.A. The cells were cultured in RPMI1640 (Sigma) medium supplemented with 10% fetal
calf serum. Generally, cells are separated into singlecell suspensions by a gentle pipetting action, then
counted using trypan-blue exclusion on a
hemacytometer, After counting, dilutions are made to
give the appropriate cell densities for inoculation
473

January 24, 2009
ISBN : 978 979 19201 0 0
onto the microtiter plates. A 100 L aliquot of

complete medium is added to cell-free wells. Cells
from all cell lines are counted, diluted and inoculated
onto microculture plates. The microtiter plates
containing the cells are preincubated for
approximately 24 hours at 37C to allow stabilization
prior to addition of drug. After that, for initial
screening of pure compounds, each agent is routinely
tested at five 10 fold dilution, starting from a
maximum concentration of 10-4M and immediately
100 L aluquots of each dilution are added to the
appropriate microtiter plates wells. During
development of these procedures, drug incubation
time was 4 days at 37C in an atmosphere of 5% CO2
and 100% relative humidity. The plates were then
assayed for cytotoxicity using the microtitration of 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
bromide (MTT) assay (Sigma,) [11]. Controls that
contained only cells were included for each sample.
Cytotoxicity (CD50) was expressed as the
concentration that reduced the absorbance of treated
cells by 50% with reference to the control, untreated
cells. Tamoxifen were used as the standard control.
Qualitative Antimicrobial Assay
Eight pathogenic microbials were used to test the
biological properties of the Schiff bases and their
complexes at Laboratory of Molecular and Cell
Biology, Institute of Bioscience, Universiti Putra
Malaysia. They were Methicillin resistant
staphylococcus (MRSA), Bacillus subtilis wild type
(B29), Subtilis mutant (mutant defective DNA repair,
B28), Pseudomonas aeruginosa (60690), Candida
albicans (C.A.), Aspergillus ochraceous (398),
Saccharomyces cerevisiae ( 20341) and Candida
lypolytica (2075). Antimicrobial activity of each
sample was qualitatively determined by a modified
disc diffusion method [12]. A lawn of
microorganisms was prepared by pipetting and
evenly spreading inoculum (10-4 cm3, adjusted
turbidometrically to 105 106 cfu/cm3 (cfu: colony
forming units) on to agar set in Petri dishes, using
Nutrient agar (NA) for the bacteria and potato
dextrose agar (PDA) for fungi. Whatman No. 1 filter
paper discs of 6mm diameter were impregnated with
stock solution of the compound (100mg/cm3) and
dried under sterile conditions. The dried discs were
then placed on the previously inoculated agar surface.
The plates were inverted and incubated for 24 hours
at 30C for bacteria and 37C for fungi.
Antimicrobial activity was indicated by the presence
of clear inhibition zones around the discs.
Commercially available Streptomycin (Sigma) was
Proceeding Book
used for the antibacterial control while Nystatin

(Sigma) was used as the antifungal control.
Quantitative Antimicrobial Assay
Compounds that showed positive (diameter >15 mm)
anti-microbial inhibition with the disc diffusion assay
were subjected to the broth dilution method for the
quantitative
measurement
of
microbiostatic
(inhibitory) activity as described previously [13]. The
lowest concentration that completely inhibited visible
microbial growth was recorded as the minimum
inhibitory
concentration
(MIC,
g/cm3).
Streptomycin and Nystatin were used as controls
standard

Cytotoxic Assay
All the Schiff bases and complexes were evaluated
in-vitro using CaOV-3 (Human ovarian cancer cells
), MDA-MB-231 (Human breast carcinoma cells with
negative estrogen receptor) and HEP-G2 (Human
liver carcinoma cells) to see if they had potential use
as anticancer agents. Measurement for cytotoxicity
was in CD50, where CD50 refers to cytotoxic dose at
50% i.e. the concentration required to reduce growth
of cancer cells by 50%. Compounds having CD50
values of less than 5 g cm-3 are considered highly
active and 5-10 g cm-3 are moderately active.
Compounds with CD50 from 10-20 g cm-3 are
classified as having weak cytotoxic activity while
those compounds having CD50 values of more than
20 g cm-3 are considered as inactive. The results
show that all screening results against selected cancer
cells are shown in Table 1. All the Schiff bases and
complexes were not active against all the cancer cell
lines tested.
The cytotoxic potential of the compounds
containing thiophene is well supported by other
researchers [14-17]. An earlier study with the related
compounds [18], SB2ATP, SB3ATP, Co(SB2ATP)2,
Cu(SB2ATP)2, Cu(SB3ATP)2, Zn(SB2ATP)2 and
Cd(SB2ATP)2 showed high activity toward human
breast carcinoma with positive estrogen receptor
(MCF-7). Unfortunately, comparison with human
breast carcinoma with positive estrogen receptor
(MCF-7) was unable to be done as cells were
unavailable.
The results showed that the Schiff bases
synthesized by condensation of SBDTC with furyl
groups (5-methyl-2-furyldehyde and 2-furyl-
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January 24, 2009
ISBN : 978 979 19201 0 0
methylketone) [6] were highly active against CEMSS (Human cell T-lymphoblastic leukemia) with a
CD50 value of 2.0 mg cm-3 when chelated to Zn(II)
[Zn(NS)2]. Furthermore, [Cd(NS)2] was moderately
active with a CD50 value of 4.95 mg cm-3 but none of
the compounds were found to be active against HT29
(Human
colon
adenocarcinoma
cells).
Unfortunately, comparison with CEM-SS (Human
cell T-lymphoblastic leukemia) and HT-29 (Human
colon adenocarcinoma cells) was unable to be done

as those cells were unavailable also.
It is clear that small changes in the backbone
of the structure of a ligand, with benzyl ring, were
unable to bring about great changes in the ability of
the complex to act as an anticancer agent against
different cell lines. However, it is hoped that some
series of complexes would show activity with cancer
cell lines that were not tested, i.e MCF-7, CEM-SS
and HT-29.
Table 1 Screening test against CaOV-3 (Human Ovarian Cancer cells ), MDA-MB-231 (Human breast carcinoma
cells with negative estrogen receptor) and HEP-G2 (Human Liver carcinoma cells)
Compounds
NS'
Co(NS')3
Ni(NS')2
Cu(NS')2. H2O
Zn(NS')2
Cd(NS')2
Standard
Tamoxifen
CaOV-3
1.0
-
Antimicrobial Assay
The qualitative results are shown in Table 2. it was
clearly seen that after chelation, the antimicrobial
activity decreased for NS against B29, where the
activity was similar. Among all the metal complexes,
only [Cu(NS)2.H2O] complexes showed weak
activities against more than two types of microbes.
None of the compounds showed any antimicrobial
activity towards S.T and 60690. Ni(NS)2 showed
CD50 (g/ml)
MDAMB-231
2.3
inactive
HEP-G2
3.5
weak activity against 398. Finally B29 was less

resistant with NS complexes. It can be deduced that
the presence of a bulky group can enhance the
activity. The same pattern has also been observed for
amoebicidal activity of palladium(II) complexes
derived
from
thiophene-2-carboxaldehyde
thiosemicarbazones [26]. However, a series of
thiophene derived dithiocarbazate Schiff bases and its
complexes can enhance the antimicrobial activity
only
after
chelation
with
Cu2+.
Table 2 Qualitative antimicrobial assay results a (diameter in mm)
Sample
NS'
Co(NS')3
Ni(NS')2
Cu(NS')2. H2O
Zn(NS')2
Cd(NS')2
Streptomycin
(antimicrobial
control)
Nystatin
(antifungal control)
Proceeding Book
Bacterial strains
MRSA
10
-
25
B29
9
9
-
S.Typhimurium
60690
10
-
9
-
15
17
20
Fungal Strains
C.A
398
20341
6
-
6
8
23
24
28
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ISBN : 978 979 19201 0 0
Methicillin resistant Staphylococcus (MRSA); Bacillus subtilis wild type (B29); S.typhimurium Salmonella
typhimurium; Pseudomonas aeruginosa (60690); Candida albicans (C.A); Aspergillus ochraceous (398);
Saccharomyces cerivisiae (20341)
a
Diameter of 15 mm and above considered active;
- inactive
Conclusion
The biological activity results showed that the
thiophene derivatives were not promising undergo
against the targeted pathogens/cell lines. Small
changes in the backbone of the structure of a ligand
(with phenyl ring) was unable to bring about great
changes in the potential bioactivity of the ligands or
their complexes. Furthermore, the presence of the
thiophene ring in the compounds synthesized did not
show any enhanced biological activity as compared
to similar compounds with a furyl group. This was in
contrast to results found for acetylthiophene isomers
(2-acetylthiophene and 3-acetylthiophene).
Acknowledgements
We thank the Department of Chemistry, Universiti
Putra Malaysia for support and the provision of
laboratory facilities. Also to Clinical Genetics Unit,
Department of Human Growth and Development,
Faculty of Medicine and Health Science and the
Laboratory of Molecular and Cell Biology, Institute
of BioSciences, Universiti Putra Malaysia for the
Biological studies. This work has been carried out
with the financial support from Ministry of Science
and Environment, Malaysia, under the Intensification
of Research in Priority Area (IRPA) program (Grant
no 09-02-04-0755-EA001)
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[2] Akbar Ali, M., Mirza, A. H., Nazimuddin, M.,
Ahmed, R., Gahan, L. R. and Bernhardt, P. V. (2003)
Synthesis and characterization of mono- and bisligand zinc(II) and cadmium(II) complexes of the di2-pyridylketone
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[3] Akbar Ali, M., Mirza, A. H., Nazimuddin, M.,
Rahman, H. and Butcher, R. J. (2001) Mono- and bis-
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chelated nickel(II) complexes of the di-2pyridylketone Schiff base of S-methyldithiocarbazate

and the X-ray crystal structure of the bis[S-methyl[beta]-N-(di-2-pyridyl)methylenedithiocarbazato]nickel(II)
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[4] Akbar Ali, M., Mirza, A. H., Voo, C. W., Tan, A.
L. and Bernhardt, P. V. (2003) The preparation of
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pentadentate N3S2 ligand formed from 2,6diacetylpyridine
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novel dimeric [Zn2(SNNNS)2] complex. Polyhedron.
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[5] Ali, M.A., Mirza, A. H., Tan, A. L., Wei, L. K.
and Bernhardt, P. V. (2004) The preparation and
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complexes of the 2,6-diacetylpyridine Schiff bases of
S-alkyl/aryl-dithiocarbazates and the X-ray crystal
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[6] Tarafder, M. T. H., Khoo, T. J., Crouse, K. A.,
Ali, A. M., Yamin, B. M. and Fun, H. K. (2002)
Coordination chemistry and bioactivity of Ni2+, Cu2+,
Cd2+ and Zn2+ complexes containing bidentate Schiff
bases derived from S-benzyldithiocarbazate and the
X-ray crystal structure of bis[S-benzyl-[beta]-N-(5methyl-2-furylmethylene)dithiocarbazato]
cadmium(II). Polyhedron. 21 (25-26) 2547-2554.
[7] Tarafder, M.T.H., Chew, K. B., Crouse, K. A.,
Synthesis and characterization of Cu(II), Ni(II) and
Zn(II) metal complexes of bidentate NS isomeric
Schiff bases derived from S-methyldi-thiocarbazate
(SMDTC): bioactivity of the bidentate NS isomeric
Schiff bases, some of their Cu(II), Ni(II) and Zn(II)
complexes and the X-ray structure of the bis[Smethyl-[beta]-N-(2-furylmethyl)methylenedithiocarbazato]zinc(II) complex.
Polyhedron. 21 (27-28) 2683-2690.
[8] Tarafder, M. T. H., Khoo, T. J., Crouse, K. A.,
Coordination chemistry and bioactivity of some
metal complexes containing two isomeric bidentate
476

January 24, 2009
ISBN : 978 979 19201 0 0
NS
Schiff
bases
derived
from
Sbenzyldithiocarbazate and the X-ray crystal structures
of
S-benzyl-[beta]-N-(5-methyl-2-furylmethylene)
dithiocarbazate
and
bis[S-benzyl-[beta]-N-(2furylmethylketone)dithiocarbazato]cadmium(II).
Polyhedron. 21 (27-28) 2691-2698.
[9] Chew, K. B., Tarafder, M. T. H., Crouse, K. A.,
Synthesis, characterization and bio-activity of metal
complexes of bidentate N-S isomeric Schiff bases
derived from S-methyldithiocarbazate (SMDTC) and
the X-ray structure of the bis[S-methyl-[beta]-N-(2furyl-methylketone)dithiocarbazato]cadmium
(II)
complex. Polyhedron. 23 (8) 1385-1392.
[10] Tarafder, M. T. H., Kasbollah, A., Crouse, K.
A., Ali, A. M., Yamin, B. M. and Fun, H. K. (2001)
Synthesis and characterization of Zn(II) and Cd(II)
complexes
of
S-benzyl-[beta]-N-(2pyridyl)methylenedithiocarbazate
(HNNS):
bioactivity of the HNNS Schiff base and its Zn(II),
Cu(II) and Cd(II) complexes and the X-ray structure
of the [Zn(NNS)2] complex. Polyhedron. 20 (18)
2363-2370.
[11] Mosmann, T. (1983) Rapid colorimetric assay
for cellular growth and survival: Application to
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Immunological Methods. 65 (1-2) 55-63.
[12] Bauer, A.W.,Kirny, M.D.K., Sherries, J.C., and
Turck, M. (1996). Am. J. Clin. Pathol. 45: 493.
[13] Hufford, C.D., and Clark, A.M.(1988).
Discovery and development in the new drug for
systematic oppurtunitic infections, studies in natural
product chemistry. Elsevier 2: 421-452
[14] Singh, S., Bharti, N., Naqvi, F. and Azam, A.
(2004) Synthesis, characterization and in vitro
Antiamoebic Activity of 5-nitrothiophene-2carboxaldehyde thiosemicarbazones and their
Palladium(II) and Ruthenium(II) Complexes.
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459-465.
derivatives and Their cyclooctadiene Ru(II)

complexes. Bioorganic & Medicinal Chemistry
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[17] Chaviara, A. T., Cox, P. J., Repana, K. H.,
Pantazaki, A. A., Papazisis, K. T., Kortsaris, A. H.,
Kyriakidis, D. A., Nikolov, G. St. and Bolos, C.A.
(2005) The unexpected formation of biologically
active Cu(II) Schiff mono-base complexes with 2thiophene-carboxaldehyde and dipropylenetriamine:
crystal and molecular structure of CudptaSCl2.
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[18] Mun-Hoe Eddy Chan (2005). Synthesis,
Characterisation & Bioactivity of substituted
Dithiocarbazate Schiff Bases of Acetylthiophenyl
Isomer and Their Metal Complexes, M. Sc. Thesis,
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[15] Shailendra, Neelam Bharti, Fehmida Naqvi and

Amir Azam (2003). Synthesis, Spectral Studies and
Screening for Amoebicidal Activity of New
Palladium(II) Complexes Derived from Thiophene-2carboxaldehyde Thiosemicarbazones, Bioorganic &
Medicinal Chemistry Letters, 13: 689692.
[16] Shailendra, Bharti, N., Gonzalez Garza, M. T.,
Cruz-Vega, D. E., Castro Garza, J., Saleem, K.,
Naqvi, F. and Azam, A. (2001) Synthesis,
characterisation and antiamoebic activity of new
thiophene-2-carboxaldehyde
thiosemicarbazone
Proceeding Book
477

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ISBN : 978 979 19201 0 0
Selectivity and Cation Exchange Capacity Determination ff Zeolite

from Fly Ash
Nungki Puspita Sari, Hamzah Fansuri, Lukman Atmaja
Chemistry Department, Faculty of Mathematics and Natural Sciences
Institut Teknologi Sepuluh November (ITS) Surabaya
Keputih Sukolilo Surabaya, East Java, Indonesia
Corresponding Author: h.fansuri@chem.its.ac.id
Abstract
Cation exchange capacity of Zeolite A, synthesized from fly ash by using a two step process namely
fusion and then followed by hydrothermal, was investigated by ammonium acetate and barium chloride
methods. Ammonium acetate method is the common way to measure cation exchange capacity of
zeolites. However the Barium chloride was reported as having an advantage than the ammonium acetate
because the exchange process is not an equilibrium reaction since the exchange product is a non water
soluble salt. The experimental results give quite different exchange capacity. The Barium method found
that the capacity is 1.15 meq/g while the ammonium method found 3.52 meq/g. The result disparity is
due to the pore opening of zeolite A which is not large enough to be accessed by large barium ions and
therefore not all exchangeable cation can be exchanged by the barium ion. The selectivity, acquired
from the ratio of selectivity coefficient of the cation, of single component system follows the order Ca2+
> K+ >NH4+> Mg2+. Meanwhile, in a multi-component exchanged cation is in the order of Ca2+ > Mg2+
> NH4+>K+. It was found that higher valence cations are more selective than the lower one.
Keyword: cation exchange capacity, fly ash, selectivity, zeolite
Introduction
Fly ashes are mainly produced from coal
combustion. They contains silicates and aluminates,
which are the main components of zeolite. Many
zeolites were successfully synthesized from fly ash
such as zeolite X [1, 2], Na-P1 [3], zeolite A [1],
zeolit K-H [4], Analcime, Chabazite, Cancrinite,
Gismodine, and Gmelinite [5].
Zeolites have capability to exchange their
cation which is proportional to Al3+ concentration in
their framework. Structure with lower Si/Al ratio has
higher exchangeable cation. Their framework stability
increases by the increase of Si/Al ratio. Zeolite A is a
synthetic zeolite that has high cation exchange
capacity (CEC) due to its high Si/Al ratio. Cation
exchange capacity is the most useful nature of
zeolites.
Garca-Sosa and Solache-Ros [6] reported
that zeolite A with Si/Al ratio = 1 has theoretical and
experimental CEC 5,3 and 4,06 meq/g, respectively.
The authors determined the CEC using ammonium
acetate method. Lower CEC (3,5 meq/g) of zeolite A
which was synthesized from fly ash was reported by
Wang et al. [7].
Several experiments have been reported in
relation to cation selectivity of zeolites. Langella et.al
[8] found that NH4+ and Pb2+ selectivities in
Proceeding Book
clinoptilolite are better than Cu2+, Zn2+ and Cd2+. The

selectivity order is NH4+> Pb2+> Na+> Cd2+> Cu2+
Zn2+. Whereas Inglezakis et.al [9] reported the cation
selectivity of clinoptilolite at total concentration of
cation 0,01 N and acidity 2 in both single- and
multicomponent solution follow the order Pb2+>
Fe3+> Cr3+ Cu2+. On the other hand selectivity in
single metal solutions where acidity is not adjusted
follow the order of Pb2+>Cr3+>Fe3+Cu2+. When the
zeolite was analchime, the cation exchange selectivity
follows the order Pb2+> Cu2+> Zn2+> Ni2+ [10]. Thus,
it was shown that different zeolites will have different
cation exchange selectivity.
This paper reports the experimental cation
exchange capacity and cation selectivity toward Ca2+,
Mg2+, NH4+, K+ of the zeolites synthesized from fly
ash.
Materials And Methods

Materials
Chemicals that were used in this experimet are
BaCl2.2H2O (Merck, pa), aqua DM, CH3COONH4
(Merck, pa), KCl (Mallincrodt, pa), MgCl2.6H2O
(pa), CaCl2.2H2O (pa), aquades, NaOH (Merck,pa),
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ISBN : 978 979 19201 0 0
NaAlO2 (Riedel-de Han, Al2O3 50-56 %; Na2O 4045%; Fe2O3 maksimum 0,05 %), tecnical ethanol.
Methods
The synthesis of Zeolite A
The zeolite A used was syntesized from fly
ash according to a method which was reported by
Sudarno [11]. Firstly, the fly ash was fused with
NaOH at 2:3 mass ratio of fly ash to NaOH in a
muffle furnace at 600oC for 2 hours. Then, the fused
mass was allowed to cooling down to room
temperature in a desiccator. When the mass reach
room temperature, it was dissolved in 127.5 mL of
water and stirred for 12 hour. Un-dissolved solids
were separated from the solution by filtration and the
composition of the filtrate was adjusted so the molar
ratios of SiO2/Al2O3, Na2O/SiO2, H2O/Na2O becomes
1.64, 8.09 and 56.51, respectively. The adjusted
solution then was crystallized in a hydrothermal
reactor at 100oC for 12 hours. The crystal products
were filtered, washed with aqua DM until the pH of
the filtrate was 10 and then dried at 100oC for 24
hours. X-ray diffraction technique was used to
characterize the product.
A similar product of zeolite A, which was
synthesized from TEOS (Tetra Ethyl Ortho Silicate)
and NaAlO2, was also prepared as a reference.
Cation Exchange Capacity (CEC) determination
The CEC of zeolites were determined using
Barium chloride and Ammonium acetate methods. In
barium acholired method, half gram (0.50 g) of
zeolite sample were added into a 5 mL barium
chloride solution 0,5 N in a conical flask. The mixture
was shaken for 24 hours. Then, the solution was
sentrifuged at 1000 rpm for 15 minutes to separate the
supernatant from the zeolite. Then, 10 mL of barium
chloride solution 1 N was added to the zeolite and
shake for another 2 hours. The zeolite was separated
and washed with 20 mL ethanol 96%. This procedure
saturated the zeolite with Ba2+. The Ba2+ saturated
zeolite was then added into 22,5 mL of ammonium
CEC (meq / 100 g ) = (mgL1cation)
acetate 1 M and shaken for 24 hours. The supernatant

was separated from the zeolite by centrifugation and
then analyzed with ICP-AES [12] for Ba2+ ion
concentration. In the ammonium acetate procedure,
the barium chloride was replaced by potassium
chloride.
The Cation Exchange Capacity (CEC) was
determined by calculating the number of equivalents
of Ba2+ or K+ replaced by ammonium ion (NH4+).
Cation Selectivity Determination
One and a half gram of zeolite was added to
a conical flask containing 50 ml of single and mixedmetal solutions at total concentration of 1 N and
shook for 24 hours. The following solutions were
used in cation selectivity determination:
(a) Solutions of single cation (KCl, CaCl2, MgCl2,
NH4CH3COO) where the concentration of each
cation was 1 N.
(b) Four-component
solution
where
the
concentration of each cation was 0.25 N.
Liquid samples were taken from the continuously
shakes mixture at 1, 3, 6, 12, 24 hours where total
volume of the samples were not exceeding 4% of the
total volume of initial solution. The concentration of
metal cations in the liquid samples was measured
with ICP AES and ammonium was determined
spectrophotometrically using Nessler reagent.

Cation Exchange Capacity (CEC)
CEC is a calculated value that is an estimate
of materials ability to attract, retain, and exchange
cation elements. In this experiment, CEC of zeolite
products were determined by Barium Chloride
method [12]. A few modifications were used in this
method. Barium that enter framework were
exchanged with ammonium. Ammonium acetate
method is used for comparator of barium chloride
method. The CEC was calculated by Equation (3.1).
Table 1 shows the CEC values of zeolite A.
V ( L)
100 g
MECation zeolite( g )
(3.1)
Table 1 Cation Exchange Capacity of Zeolite from Fly Ash and TEOS
CEC
CEC
CEC calculated
(meq/ 100 g)a
(meq/ 100 g)b
(meq/100 g)c
Zeolite from TEOS
189,72
320,94
530
Zeolit from fly ash
115,83
352,27
a. barium chlorida method, b. ammonium acetate method, c. Garca-Sosa and Solache-Ros (2001)
Sample Zeolite
Proceeding Book
479

January 24, 2009
ISBN : 978 979 19201 0 0
Table 1 shows that CEC of zeolite from

TEOS and fly ash using ammonium acetate method is
higher than using barium chloride method. It
happened because particle size of potassium ion is
smaller (r(K+) = 133 pm) than barium (r(Ba2+) = 143
pm) so the potassium ion can enter the cation site in
the pore the zeolite easier than the barium ion.
The Table also shows that the CEC of zeolite
from TEOS is higher than those from fly ash while it
is lower for the zeolites synthesized from fly ash.
Zeolite from TEOS contains higher purity zeolite A
while those from fly ash has lower zeolite A purity

where the impurity might be other zeolites with
smaller apertures to the site of exchangeable cation.
Thus, only smaller cations have higher probability to
enter the sites and replace the cations. The difference
in zeolite A purity can be seen from the diffractogram
of the zeolites in Figure 1.
(a)
(b)
JCPDS-ICDD
No PDF 39-0222
Figure 1 The X-ray diffractograms of zeolite A from: a) fly ash and b) TEOS
The main impurities in the zeolite A
synthesized from fly ash are amorphous phases.
The phases are clearly shown as the baseline of
zeolite A from fly ash is more curvature than those
Proceeding Book
from TEOS. These phases may contain very fine

crystal of other types of zeolites which can
exchange their cations and thus added to the total
exchangeable cations in the zeolite product.
480

January 24, 2009
ISBN : 978 979 19201 0 0
The difference in the CEC might also been

caused by the use of TEOS as a source material in
the zeolite synthesis. The hydrolysis of TEOS
which was occurred during the hydrothermal
process produced ethanol that may be trapped in the
cation exchange sites so that exchange cations
cannot enter the site.
The same results were also found when the

two CEC determination methods were used for
other zeolites from fly ash, prepared by Hidayati
[13], Nafiah [14] and Muasyaroh [15]. All zeolite
synthesized from fly ash shows higher CEC value
when determined using ammonium acetate than
using barium chloride method as shown in Table 2.
Table 2 CEC Comparison using Ammonium Acetate and BaCl2 Method [12-14]
KOH
Reaction Condition
Initial
Initial
Hydrothermal Hydrothermal
time
temperature
CEC(a)
(mek/100 g)
CEC(b)
(mek/100 g)
Mineral Phases
3M
1 Hours
180C
325,81
6,80
K-F
3M
3,5 Hours
180C
309,11
9,40
M,Q, K-F,K-P
3M
5 Hours
180C
397,80
7,20
K-F
3M
3,5 Hours
100C
230,39
6,04
M,Q, K-F, K-G,K-P
3M
3,5 Hours
120C
250,94
5,52
M,Q, K-F, K-G,K-P
1M
3,5 Hours
180C
261,00
6,95
K-M, M
5M
3,5 Hours
180C
134,10
4,03
K-D
(a) Ammonium acetate method; (b) BaCl2 method
M: Mullite; Q: Quartz; K-F: zeolite K-F (LTF) ;K-P: K-Phillipsite; K-G: K- Chabasite; K-M: zeolite K-M; K-D:
Kaliophilite
equilibrium state of the exchange reaction which
Cation Selectivity
shows the degree of exchange can be studied from
Cation exchange reaction in zeolites can
the concentration of sodium ion in the exchange
be written as Equation 3.2. Initially the sodium ions
solution at the equilibrium state. Equation 3.3 and
are in the cation site of the zeolites. When they are
3.4 are examples of the reaction using cations with
replaced by the exchange cation in a solution, the
different oxidation states. They show that cation
sodium ion will be exiled from the zeolite and
with higher oxidation number can exchange more
available in the exchange solution. Therefore, the
sodium ion than the lower ones.
(nNa)-Zeolite + An+
Na-zeolite + KCl
(2Na)-zeolite + CaCl2
= A-zeolite + nNa+...................................................
= K-zeolite + NaCl .................................................
= Ca-Zeolite + 2NaCl .............................................
Figure 2 shows sodium extracted by Mg2+,

Ca , K , and NH4+ at the equilibrium state. The
extraction depends on the selectivity of the
exchange reaction toward the incoming cations and
hence it means that the exchange selectivity follows
the order Mg2+>NH4+>K+Ca2+.
Interesting result is shown by Mg2+
because the cation theoretically has higher
capability to exchange the sodium ion than NH4+
and K+ since it has higher oxidation number. By
virtue of the valence, magnesium should be capable
to exchange with sodium in the same manner with
calcium. Hence it is concluded that it may be
2+
Proceeding Book
(3.2)
(3.3)
(3.4)
precipitated during the exchange reaction since the

pH of the zeolite is high. As aforementioned, the
zeolite was washed until the pH was 10.
481

January 24, 2009
ISBN : 978 979 19201 0 0
+
K
2+
Ca
+
NH4
180
Sodium extracted (meq/L)
170
Mg
2+
Table 4 Selectivity Coefficient in multi-component

system
KK/Na
1.38
160
KMg/Na
3.42
KNH4/Na
3.04
KCa/Na
8.61
150
140
130
0
10
15
20
25
Time (hours)
Under alkali condition, magnesium

precipitates to form Mg(OH)2. In comparison to
calcium, the Mg(OH2) has smaller Ksp (7,1 10-12)
6,5 10-6). Therefore,
than Ca(OH)2 (Ksp=
although the condition of exchange is the same,
Mg2+ precipitates easier than Ca2+.
Numerical value of cation selectivity dan
be calculated using Equation 3.5. Table 3 shows the
calculated selectivity based on experimental
exchange data.
KC / A =
[RC ]Z [A]Z
[C ]Z [RA]Z
A
(3.5)
Table 3 Selectivity coefficient in single component

system
KK/Na
0.77
KMg/Na
0.30
KNH4/Na
0.55
KCa/Na
15.68
The cation exchange raction in multicomponent system gives better insight into the real
cation selectivity where each cation compete with
others in the same system. As in a single
component system, the selectivity in multicomponent system was investigated based on the
amount of extracted sodium from the zeolite as
shown in Figure 3.3. The Figure shows that the
equilibrium occurs at 3 hours
Table 4 shows the selectivity coefficients
of all cations used in this experiment. The
selectivity follows the order Ca2+ > Mg2+>
NH4+>K+. Hence the order follows the rule that the
ion exchange prefer higher valence cation.
Therefore, calcium and magnesium are more
selective than ammonium and potassium as
mentioned by Helferich [16].
Proceeding Book
210
Sodium extracted (meq/L)
Figure 2 Sodium extracted in single component

system
200
190
180
170
10
15
20
25
waktu (jam)
Figure 3 Sodium extracted on multicomponent

system
Conclusions
1.
The CEC of zeolite from fly ash is 115,83

meq/100g using barium chloride method and
352,27 meq/100g using ammonium acetate
method. The difference is due to different in
cation size of B2+ in barium method and K+
used in ammonium acetate method.
2. Cation selectivity in single component system is
following the order Ca2+ >K+> Mg2+>NH4+.
Magnesium is the lowest because the zeolite is
alkaline that cause the formation of
magnesium hydroxide precipitate.
3. Cation selectivity in multi-component system is
following the order Ca2+ > Mg2+>K+ > NH4+.
Cations with higher oxidation state have higher
selectivity than the lower ones.
Acknowledgment
The authors acknowledge The Ministry of
Research and Technology for research grant under
the scheme of Insentif Riset Terapan in 2007.
482

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ISBN : 978 979 19201 0 0
9.
References
1. Ojha, K., Pradhan, N.C. and Samanta, A.N.
(2004), Zeolite from fly ash: synthesis
and characterization, Mater Sci B, Vol
27, No 6, p. 55564.
2. Chang, H.L. and Shih, W.H. (2000), Synthesis
of Zeolites A and X from Fly Ashes and
Their Ion-Exchange Behavior with Cobalt
Ions, Ind. Eng. Chem. Res., Vol 39, p.
4185-4191
3. Woolard, C.D., Petrus, K. and van der Horst, M.
(2000), The use of a modified fly ash as
an adsorbent for lead, Water SA , Vol 26
(4), p. 531536.
4. Mimura, H.K, Yokota, K., Akiba, Y. and
Onodera, Y. (2001), Alkali hydrothermal
synthesis of zeolites from coal fly ash and
their uptake properties of cesium ion, J
Nucl Sci Technol; Vol 38(9), p. 766772.
5. Elliot, A.D and Zhang, D.K. (2005), Controlled
Release Zeolite Fertilizers: A Value Added
Product Produced from Fly Ash,
www.flyash.info/2005, Perth.
6. Garca-Sosa. I and Solache-Ros. M. (2001),
Cation-exchange capacities of zeolites A,
X, Y, ZSM-5 and Mexican erionite
compared with the retention of cobalt and
cadmium, Journal of Radioanalytical and
Nuclear Chemistry, Vol. 250, No. 1, p.
205206.
7. Wang, C.F., Li, J.S., Wang, L.J. and Sun, X.Y.
(2008),
"Influences
of
NaOH
Concentrations on Synthesis of Pure-Form
Zeolite A from Fly Ash using Two-Stage
Method", Journal of Hazardous Materials,
Vol. 155, p. 58-64.
8. Langella, A., Pansini, M., Cappelletti, P., de
Gennaro, B. and de Gennaro, .M. (2000),
NH4+, Cu2+, Zn2+, Cd2+ and Pb2+ exchange
for Na+ in sedimentary clinoptilolite, North
Sardinia, Italy,
Microporous and
Mesoporous Materials, Vol. 37, p. 337
343.
Proceeding Book
10.
11.
12.
13.
14.
15.
16.
Inglezakis, V.J, Loizidou, M.D. and

Grigoropoulou,
H.P.
(2003),
Ion
exchange of Pb2+, Cu2+, Fe3+, and Cr3+ on
natural
clinoptilolite:
selectivity
determination and influence of acidity on
metal uptake, Journal of Colloid and
Interface science, Vol. 261, p. 49-54.
Tangkawanit, S., Rangsriwatananon, K. and
Dyer, A. (2005), Ion exchange of Cu2+,
Ni2+, Pb2+ and Zn2+ in analcime (ANA)
synthesized
from
Thai
perlite,
Microporous and Mesoporous Materials,
Vol. 79, p. 171 175.
Sudarno (2008), Pengaruh Komposisi NaOH
Pada Konversi Abu Layang Batubara
Paiton Menjadi Zeolit A, Skripsi Sarjana
Kimia, ITS, Surabaya.
Gillman, G.P. (1979), A Proposed Method for
the Measurement of Exchange Properties
of Highly Weathered Soils, Aust. J. Soil
Res., Vol. 17, p. 129-139.
Hidayati, R.E, (2008), Sintesis zeolit dari abu
layang batubara: kajian pengaruh waktu
hidrotermal awal terhadap pembentukan
zeolit, Tesis Magister Kimia, ITS,
Surabaya.
Nafiah, C. (2008), Pengaruh Komposisi KOH
pada Sintesis Zeollit dari Abu Layang
Batubara, Tesis Magister Kimia, ITS,
Surabaya.
Muasyaroh, D. (2008), Pengaruh Suhu
Hidrotermal Awal terhadap Pembentukan
Zeolit dari abu Layang Batubara, Tesis
Magister Kimia, ITS, Surabaya.
Helferich, F. (1962), Ion Exchange, McGrawHill Book Company, Inc., New York.
483

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ISBN : 978 979 19201 0 0
Relationship Pattern Between SiO2/Na2O Ratio

and Microstructure of Fly Ash Based Geopolymer
Mochamad Zakki Fahmi, Lukman Atmaja*, Hamzah Fansuri
MasterDegree StudyProgram, Chemistry Departemant, Faculty of Mathematics and Natural Sciences Sepuluh
Nopember Institute of Technology Surabaya, Sukolilo Surabaya 60111
* Corresponding author
Email address : lukman.at@gmail.com
Abstract
Converting fly ash to geopolymers is one of the most important scheme to reduce its dengerous effect to
environment. The initial molar contents of SiO2, Na2O and Al2O3 of geopolymer systems gave some
influence to geopolymer matrices. This research studied that the Na2O gave effect to physical properties
of Cilacap and Asam-asam fly ash-based geopolymers, which increase SiO2/Na2O ratio made positive
effect to compressive strength and caused the microstructure of geopolymers more compact and
homogen. Although NaOH (main source for variation SiO2/Na2O ratio in this research) is needed for
disolve fly ash particles, high content of sodium cation can discontinu geopolymersation process. The
effect of sodium cation has been investigated by quantiative analysis FTIR as well as their
microstructure by SEM
Key word : fly ash, geopolymer, microstructur, SiO2/Na2O ratio
Introduction
Geopolymers , a kind of
inorganic
polymer, are alumnosilicate materials which exhibit
excellent physical and chemical properties. Since
1979, when davidovits first introduced the term
geopolymers to designate a new class of three
dimensional alumino-silicate materials (Davidovits,
1979), the interest toward the implementation of
new technologies for manufacture of great
potentialities geopolymers based products has
steadily grown. Geopolymers also exihibit a diverse
range of potential applications, including precast
structures and non-structural elements, concrete
pavements and products, containment and
immobilisation of toxic, hazardous and radioactive
wastes, advanced structural tooling and refractory
ceramics, and fire resistant composites used in
buildings, aeroplanes, shipbuilding, race cars and
nuclear power industry (Komnitsas and Zaharaki,
2007).
The synthesis of geopolymers takes place
by polycondensation and can start from a variety of
raw materials. Davidovits (1994, 1995), Schmcker
and Mackenzie (2005), Xu et al. (2001,2002), Van
Jaarsveld and van Deventer (1999,2003) and
Duxson et al. (2005) use metakaolinite to obtain
geopolymers by reaction with alkaline (Na or K)
solution. Meanwhile, Swanepoel and Strydom
Proceeding Book
(2002),
Fernndez-Jimnez
and
Palomo
(2003,2005), Andini et al.(2007), lvarez-ayuso et
al (2007) and Criado (2007) have proven that
geopolymers could be obtained starting material
from many raw alumino-silicates, including coal fly
ash as starting material. Also in this case the
polycondensation takes place by reaction with
alkaline solution.
In material contruction, fly ash based
geopolymers is prefered over Portland cement
because can reduce the emission of greenhouse
gases into the atmosphere (essentially CO2 and NOx;
the manufacture of one tonne of cement generates
approximately one tonne of CO2) (Criado, 2007).
Beside that, Rangan et al. (2005) was estimated that
production of fly ash based geopolymer concrete
may be 10-30% cheaper than that of Portland
cement concrete.
Fly ash based geopolymers products and its
process depend on many aspects, the SiO2/Al2O3,
SiO2/Na2O and H2O/ Na2O ratio was commonly
chemical aspects to make geopolymers materials
with excellent physical and chemical properties.
lvarez-ayuso (2007), Alfiyah (2008), Muslihah
(2008) and Mulyanto (2008) explain that the
SiO2/Na2O ratio in alkaline solution affects the
degree of polymerisation of the dissolved species.
The increase of NaOH contain lead to increasing the
dissolution of alumino-silicate materials and,
484

January 24, 2009
ISBN : 978 979 19201 0 0
consequently, geopolymers product will have

excellent mechanical strength. Fernndez-Jimnez
and Palomo (2005), Lodeiro dkk.(2006) and De
Silva dkk.(2007) have shown that increasing
SiO2/Na2O ratio affects the production of
geopolimer because it increases porosity and
heterogenity.
The SiO2/Al2O3, SiO2/Na2O and H2O/
Na2O ratio and other chemical aspects can also
influence other physical properties, such as
microstructure and compressive strength. The
present paper is studied the microstructures of fly
ash based geopolymers derived from the activation
of fly ash by concentrated alkaline solution (made
from mixed sodium hydroxide and sodium silicate).
Variation effect of SiO2/Na2O ratio is expected to
show different geopolymer morphology and could
be related to its compressive strength.
fly ash from the Asam-asam steam power plant in

Indonesia were used in the present study. The ashs
chemical composition are given in table 1.
The ash activated with a series of alkaline
solution that consist of 98% NaOH pellet supplied
by Merck and sodium silicate using following
composition : 37.99% Na2O, 19.16% SiO2 and
28.07% H2O. H2O that use in the present study was
destilated water. Composition of the systems studied
is shown in table 2. Sodium hidroxsida content in
the solution was varied to have different SiO2/Na2O
ratio.
Method
The properties of geopolymer matrices
normally depend on the consistency of geopolymer
materials and the consistency itself is influenced by
the amount of enhanced water. Therefore, to make
consistency factor can be disregarded, all
geopolymer reactant should have similar
consistency. In this study, method for consistency
test was adopted from Cindaprasirt (2006). With
same concistency, Solid/Liquid ratio is constant for
whole geopolymer reactant.

Material
Class C (according to ASTM C 618-03) fly
ash from the Cilacap steam power plant and class F
Table 1.Chemical analysis of the original fly ash in precentage
Cilacap
fly ash
(%)
Asamasam
fly ash
(%)
SiO2
Al2O3
CaO
Fe2O3
K2O
MgO
Na2O
P2O5
SO3
TiO2
MnO
BaO
SrO
LOI
Total
31.5
12.4
21.4
22.5
0.75
7.87
0.27
0.12
1.06
0.76
0.27
0.24
0.09
0.49
99.72
43.7
21
4.85
22.5
0.88
2.55
0.44
0.07
0.58
0.95
0.44
0.21
0.06
1.66
99.89
LOI = loss on ignition
Table 1.Composition of geopolymer systems were studied

Fly ash Na2SiO3
NaOH(g) H2O (g)
(g)
(g)
As 1
40,38
10
20,96
10,37
As 1,5
40,38
10
12,26
9,13
As 2
40,38
10
7,92
8,46
As 2,5
40,38
10
5,31
8,13
As 3
40,38
10
3,57
7,88
Ci 1
35,39
10
12,42
9,38
Ci 1,5
35,39
10
6,60
8,38
Ci 2
35,39
10
3,40
7,97
Ci 2,5
35,39
10
1,95
7,64
Ci 3
35,39
10
0,70
7,47
*
As refers to Asam-asam and Ci refers to Cilacap
Sample*
Proceeding Book
485

January 24, 2009
ISBN : 978 979 19201 0 0
The water content of geopolymers system

is the amount of water added to the mixture of fly
ash, NaOH and Na2SiO3, so that, the paste has a
flow rate of 33 seconds when the paste was
inclinated at 6,13.
The pastes were made by mixing the fly
ash with alkaline solution, then shaped in cylindrical
container (1.5 cm and 3 cm diameter and long,
respectively) and cured in an oven at 60C for 24
hours. Geopolymer pellets were then kept in room
temperature for different curing times (7, 14, 21 and
28). Mechanical test using universal testing machine
and morphology analysis using scanning electron
microscopy (SEM), which conducted with energy
dispersive X-ray (EDX), were conducted to pellets
geopolymer in each curing time. The highest and the
lowest compressive strength of pellets from Cilacap
(Ci) and Asam-asam (As) were analyzed with
fourier
transform
infrared
(FTIR)
for
geopolymerisation paste study

Compressive Strength Analysis
Compressive strength analysis was carried
out to investigation in which composition system
that having excellent performaces. Compressive
strength results of varying geopolymer pellets were
shown in Fig.1 and Fig.2 for Cilacap and Asamasam geopolymers, respectively.
with the increase of curing times, facts, this is

indicated that geopolymerisation process still
happens during curing time and gives positive effect
to the compressive strengths.
Fig. 1. show that the increase on
SiO2/Na2O ratio for Cilacap geopolymers will
increase its comperssive strength and reach a max at
SiO2/Na2O ratio = 3, ie. 81,53 MPa. Fig. 2 was
Shown that the increase on SiO2/Na2O ratio not
always increace the compressive strength. In Fig 2.,
the highest compressive strength is owned by
geopolymers with SiO2/Na2O ratio about 2,5 (40.48
MPa). Panias et al.(2006) explained that the
increased sodium hidroxide (NaOH) concentration
of the aqueous phase of geopolymeric system cause
positive, as well as negative effects on the
mechanical properties of the geopolymeric
materials. In low concentration, NaOH is used to
dissolve Si and Al species from fly ash particles that
produce component for geopolymerisation process.
Whereas in high concentration, sodium cation,
which are normally presented at high concentrations
in the geopolymeric systems, are specifically
adsorbed ions on the surface of fly ash particles
changing the surface speciation (silanol and
aluminol). The sodium cation adsorption make
chemical bonding between the insoluble solid
particle and the geopolymeric framework takes
place in the final stage of geopolymeric process.
Thus, the resulted geopolymeric materials have low
low mechanical strength.
7 day
14 day
21 day
28 day
40
80
7 day
14 day
21 day
28 day
70
60
Compressive strength (MPa)
Compressive strength(MPa)
90
50
40
30
20
35
30
25
20
15
10
5
10
0
0.5
0
0.5
1.0
1.5
2.0
2.5
3.0
Rasio SiO 2 /Na 2 O
Figure. 1. Compressive strength result for Cilacap

geopolymers
Both Cilacap and Asam-asam geoplymers

show that the compressive strengths result increase
Proceeding Book
1.0
1.5
2.0
2.5
3.0
Rasio SiO 2/Na 2O
Fig. 2. Compressive strength result for Asamasam geopolymers
Comparing the compressive strengths

between Cilacap and Asam-asam geopolymers, it
can be seen thatt compressive strength from Cilacap
geopolymers are normally higher than Asam-asam
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January 24, 2009
ISBN : 978 979 19201 0 0
geopolymers. This fact is in line with previous

reportthat the CaO content of fly ash can give
positive effect to geopolymer products, cause Ca+
cation will form amorphously structured Ca-Al-Si
gel in geopolymeric process (Komnitsas and
Zaharaki, 2007).
The Setting time in Asam-asam
geopolymers are longer than that of Cilacap
geopolymers. Its also should be reportedthat a
pellets of Asam-asam geopolymers with SiO2/Na2O
ratio about 1 at 7 day can not be analyzed because
the result was too small and undetected. In general,
compressive strength related to SiO2/Al2O3 ratio in
Asam-asam geopolymers was higher than that of
Cilacap geopolymers and this fact plays an
important to the setting time of geopolymeric
process (De Silva, 2007).
Morphology Analysis
Morphology analysis of
Cilacap and
Asam-asam geopolymers was shown at Fig. 3. it is
clear that the increase of SiO2/Na2O ratio would
.
Proceeding Book
decrease heterogenous surface phase and increase

compact region in its morphology. This region lies
where dissolution of fly ash particle and the
geopolymeric process perfectly take place.
The figures. also show that at low
SiO2/Na2O ratio most fly ash particles had been
dissolved, but in high SiO2/Na2O ratio many fly ash
particles apparently unreacted. This phenomenon
could be due to low NaOH content at SiO2/Na2O
ratio acting as dissolveing agent of fly ash particle .
Beside unreacted ash, many internal crack
was also found in high SiO2/Na2O ratio. Internal
cracks were arising when the shorten setting time
geopolymers loose waters at curing temperature of
geopolymer pellets. Beside that, Na2SiO3 content
have potential to rise internal cracks. Hermanus and
Lapu (2001) have shown that Na2SiO3 activated
geopolymers giver more crack than NaOH activated
geopolymer. In present study, Na2SiO3 content in
every geopolymer systems is constant but NaOH
content is varied. Thus, morphology effect of
Na2SiO3 content in high SiO2/Na2O ratio more
apparent than
in
low SiO2/Na2O ratio
487

January 24, 2009
ISBN : 978 979 19201 0 0
Cilacap
Asam-asam
Ci 1 : SiO/Na2O
As 1 : SiO/Na2O =
Ci 1,5 : SiO/Na2O
As 1,5 : SiO/Na2O =
Ci 2 : SiO/Na2O =
As 2 : SiO/Na2O =
Ci 2,5 : SiO/Na2O =
As 2,5 : SiO/Na2O =
Ci 3 : SiO/Na2O =
As 3 : SiO/Na2O =
Fig. 3 SEM micrograph of Cilacap (Ci) and Asam-asam (As) geopolymers at SiO2/Na2O ratio about 1-3.
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ISBN : 978 979 19201 0 0
(a)
(b
(c)
(d
Fig. 4. Zeolite phase at As 1 (a), As 1,5 (b), Ci 2 (c)

and Ci 3(d)
(
Fig. 5. SEM micrograph and square EDX analysis of As 1 (a) and Ci
Proceeding Book
489

January 24, 2009
ISBN : 978 979 19201 0 0
(Tolah, 2008) and the reaction products after

activation (Ci 3). Original ash consisted mostly in a
vitreous phase comprising SiO2 and Al2O3. The
presence of quartz in the fly ash rise the IR spectrum
to a series of bands located at 1150, 1084, 796-778,
697, 668, 522 and 460 cm-1. The presence of mullite
is responsible for series of band at around 11801130 cm-1 and 560-550 cm-1. Thus, the bands
generated by quartz and mullite of the ash show
overlap in wavenumber between 1200 and 900 cm-1(
Criado et al., 2007).
The Effect of
sodium cation on
geopolymerisation process was shown at SEM-EDX
of As 1 and Ci 1 geopolimer (Fig. 5). In line with
previous explanation by Panias et al.(2006), square
EDX graphic show that sodium cation cause
ungeopolymerized region with uncompact and high
heterogenicity. In the same picture, Al element that
need to geopolimerisation was undetected.
FTIR Analysis
Fig. 6. shows the infrared spectroscopy
results for Cilacap fly ash from previous study
Ci 3
Cilacap Fly ash
Transmitance (%)
b
c d
a
e
f
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Fig. 6. FTIR spectra of Cilacap fly ash and Cilacap geopolymer (Ci 3 )
The band at 995 cm-1(a) in Cilacap original ash is
associated with T-O (T=Si,Al) asymmetric
stretching vibrations. The intensity at 457 cm -1(d) is
associated in all cases with T-O bending vibrations.
The band appering at 780-790 cm-1(b) corresponds
to the quartz present in the original fly ash. Finally,
the band at 547 cm-1(c) corresponds to the mullite
present in the ash. After alkaline activated, many
signal appearing at 1093 cm-1(e) and 996 cm-1(g)
were attributed, respectively, to the vitreous phase
of the quartz and unreacted phase; while the new
component appearing at around 1025 cm-1 (see Fig.
7). Criado (2007) was shown that peaks around
1025-1006 cm-1 indicate the sodium alumino-silicate
gel as result of activation.
Investigation of sodium cation to
geopolymer product can be seen on Fig. 8. in which
Proceeding Book
spectra shown quantitative FTIR analysis of Cilacap

geopolimer at SiO2/Na2O 1 and 3 is shown.
Furthermore, the lower peak at 3500 cm-1 and the
higher peak at 966 cm-1 of Ci 1 than Ci 3
geopolymer indicate to a lot of silanol content (SiOH that give peak 3500 cm-1 (h)and weak peak at
882 cm-1(j)) in Ci 3. The band at region 980-960 cm1
, which was investigated by Lee and Deventer
(2007), indicate Si-O- stretching vibration that
bonding with alkaline (Na+ or K+). Thus, higher
peak of Ci 1 geopolymer at 966 cm-1(i) shown SiONa stretching as result higher Na2O. Si-ONa
species gave bad effect, may discontinuing, for
geopolymerisation prosess. This is make more
heterogenicity of geopolymer and, consequently
lower compressive strength.
490

January 24, 2009
Transmitance (%)
ISBN : 978 979 19201 0 0
f
g
1200 1150 1100 1050 1000 950 900 850

-1
Wavenumber (cm )
Fig. 7 FTIR Spectra of Cilacap geopolymers at wavenumber range 850 -1200 cm-1
As 2.5
Asam-asam fly ash
k
400
600
800
1000
1200
1400
-1
Wavenumber (cm )
Fig. 9 . FTIR spectra of Asam-asam fly ash and Asam-asam geopolymer (2.5)
Asam-asam fly ash and geopolymer spectra
can be seen at Fig.9. Asam-asam fly ash shown that
wide peak in region 1400-827 cm-1 indicate
overlapping peaks which generated by quartz,
mullite and vitreous phase of fly ash. The weak
peaks at 790 cm-1(l) and 461 cm-1(k) were indicate,
respectively, T-O stretching of mullite and quartz
(Panias et al.,2006). Fig.10. shows same
Proceeding Book
phenomenon with Fig.8, where As 1 spectra have

lower peak at 3500 cm-1(m) and higher peak at 980
cm-1(n) than As 2,5 spectra. In this quantitative
analysis of As 1 and As 2,5 were choosen as,
respectively, the lowest and
the highest
compressive strength Asam-asam geopolymers,
respectively.
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As 1
As 2.5
30
20
-1
Transmitance (cm )
25
15
n
10
m
0
500
1000
3000 3500 4000 4500 5000 5500

-1
Wavenumber (cm )
Fig. 8 Quantitative analysis of FTIR to Asam-asam geopolymer at SiO2/Na2O 1 and 2.5.
Conclusions
Following conclusions can be made from
this study.
1. The initial molar constants of Na2O, SiO2 and
Al2O3 were given influence for geopolymers
product.
2. The Na2O content of geopolymer plays a key
part in dissolving fly ash particle, but in
inhigher content, it affects the compressive
strength and its microstructure.
3. Increase in SiO2/Na2O ratio for geopolymers
system, relatively, will increase compressive
strength and make geopolymer microstructure
more compact and homogen.
4. Sodium cation, at high content, can influence
geopolymer process as detected by FTIR
quantitative analysis.
Acknowledgement
the authors thank to Directorate of high
education republic of Indonesia for financial support
HIBAH PASCASARJANA Program.
Reference
Alfiyah, A., 2008, Synthesis and Characterization of
Semen Gresik Ltd. Fly Ash-Based Geopolimer,
Proceeding Book
Chemistry department Faculty of Mathematics

and Natural Sciences Sepuluh Nopember Institut
of Technology, Surabaya.
lvarez-ayuso, E., Querol, X., Plana, F., Vzquez,
E. dan Barra, M., 2007, Enviromental, Physical,
and structural characterization of Geopolymer
Matrixes Synthesisd from coal (co)combustion
fly ashes, Journal of Hazardous Material 154,
175-183.
Andini, S., Cioffi, R., Montagnaro, F. dan Santoro,
L.,2007, Coal Fly Ash as Raw Mmaterial for
the
Manufacture
of
Geopolymer-based
Products, Waste Management 28, 416-423.
Criado, M., Fernndez-Jimnez, A. dan Palomo, A.,
2007, Alkali Activation of Flyash: Effect Study
of the SiO2/Na2O Ratio (FTIR study part I),
Microporous and Mesoporous Materials 106,
180-191.
Davidovits, J., 1979, SPE PATEC 79, Society of
Plastic Engineering, Brookfield Center, USA.
Davidovits, J., 1994, Gepolymers: Man-Made Rock
Geosynthesis and the Resulting Development
of Very Early High Strength Cement,
Journals of Materials and Education 16, 91137.
Davidovits, J., 2005, Geopolymer Chemistry and
Sustainable Development. the Poly(Sialate)
Terminology: a very useful and simple model
for the promote and understanding of
greenchemistry, Proceeding of
the World
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January 24, 2009
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Congress Geopolymer, Saint Quentin, France,

28 june-1 july, 111-121.
De Silva, P., Sagoe-Crenstil, K. dan Sirivivatnanon,
V., 2007, Kinetics of Geopolymerization: role
of Al2O3 and SiO2, Cement and Concrete
Research 37, 512-518.
Duxson, P., Provis, J.L., Lukey, G.C., Kriven, M.W.
dan van Deventer, J.S.J., 2005, Microstructural
Characterisation
of
Metakaolin-Based
Geopolymer. Ceramic Transactions 165, 71-85.
Hermanus, P.A.Y., and lapu, A.S., 2001, Behaviour
of Bottom Ash for Aspalt Concrete Component,
department of Civil Engineeing Christian Petra
University, Surabaya.
Fernndez-Jimnez, A.M. dan Palomo, A., 2003,
Characterisation of Fly Ash : potensial
reactivityas alkaline cements, Fuel 82, 22592264.
Fernndez-Jimnez, A.M. dan Palomo, A., 2005,
Composition and Microstructure of Alkali
Activated Fly Ash Binder : effect of the
activator, Cement and Concrete Research 35,
1984-1992.
Komnitsas, K. dan Zaharaki, D., 2007,
Geopolymerisation: a review and prospect for
the minerals industry, Minerals Engineering 20,
1261-1277.
Lee, W.K.W. dan van Deventer, J.S.J., 2007,
Chemical Interactions between Siliceous
Aggregatesan and Low-Ca Alkali-activated
Cemant, Cement and Concrete Research 37,
844-855.
Lodeiro, G., Palomo, A. dan Fernndez-Jimnez, A.,
2006, Alkali-Aggregat Reaction in Activated
Fly Ash Systems, Cement and Concrete
Research 37, 175-183.
Mulyanto, H., 2008, Mixed Geopolymer from Semen
Gresik Ltd., Cilacap Power Plant and Asamasam Power Plant Fly Ash, Chemistry
department Faculty of Mathematics and Natural
Sciences Sepuluh Nopember Institut of
Technology, Surabaya.
Muslihah, 2008, Synthesis and Characterization of
Mixed Geopolymers from Semen Gresik Ltd. and
Asam-asam Power Plant Fly Ash, Chemistry
department Faculty of Mathematics and Natural
Sciences Sepuluh Nopember Institut of
Technology, Surabaya.
Panias, D., Giannopoulou, I.P. dan Perraki, Th.,
2006, Effect of Synthesis parameters on
Mechanical Properties of Fly Ash-Based
Geopolymers, Colloids and Surfaces Area :
Physicochemistry
Engineering
Aspects.
Accepted Manuscript.
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Rangan, B.V., Hardjito, D., Wallah, S.E.,

Sumajouw, D.M.J., 2005, Studies on fly ashbased geopolymer concrete, Proceedings of the
World Congress Geopolymer, Saint Quentin,
France, 28 June 1 July, pp. 133137.
Schmcker, M. dan Mackenzie, K.J.D., 2005,
Microstructure of Sodium Polysialate Siloxo
Geopolymer, Ceramic International 31, 433437.
Swanepoel, J.C dan Strydom, C.A., 2002,
Utillisation of Fly Ash in a Geopolymeric
Material, Applied Geochemistry 17, 11431148.
Van Jaarsveld, J.G.S. dan van Deventer, J.S.J.,1999,
Effect of Metal Alkali Activator on the
Properties of Fly Ash-Based Polymers,
Industrial Engineering Chemistry Research 38,
3932-3941.
Van Jaarsveld, J.G.S. dan van Deventer, J.S.J.,2003,
The Characterization of Source Materials in
Fly Ash-Based Geopolymer, Materials Latters
57, 1272-1280.
Xu, H. dan van Deventer, J.S.J., 2002.
Microstructural
Characteristion
of
Geopolymers
Synthesised
from
Kaolinite/Stilbite
Using
XRD,
MASNMR,SEM?EDX,TEM/EDX
and
HREM,
Cement and Concrete Research 32, 1705-1716.
Xu, H., van Deventer, J.S.J., Lukey, G.C., 2001.
Effect of Alkali Metal on the Preferential
Geopolymerisation
of
Stilbite/Kaolinite
Mixtures. Industrial Engineering Chemistry
Research 40, 3749-3756.
493

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ISBN : 978 979 19201 0 0
Synthesis and Characterization NiO/TS-1 Catalyst

Siti Qamariyah Khairunisa and Didik Prasetyoko
Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia.
1) Corresponding author, Phone: +62-85-649808681
email: skhairunisa@gmail.com and didikp@chem.its.ac.id
Abstract
Hydroxylation of phenol to hydroquinone and catechol is an important reaction for many industrial
applications, such as: photographic film developer, antioxidant, polymerization inhibitor, medicines,
perfumes, and etc. The production of hydroquinone and catechol from hydroxylation of phenol can be
produced by using homogeneous catalyst. However, this process is not efficient because need separation
between reactant, product, and catalyst. The alternative of this process is used Titanium Silicalite (TS-1)
as heterogeneous catalyst . TS-1 has great properties, such as high activity and selectivity to oxidation
reaction and green chemistry. Because TS-1 is hydrophobic, so the reaction rate of whole reaction is
low. The presence of nickel oxide on TS-1 can be increased the hydrophilicity and acid sites. NiO/TS-1
was prepared by impregnation method. The sample was characterized by XRD, FTIR, and
hydrophobicity techniques. The XRD analysis of NiO/TS-1 revealed that the MFI structure of the TS-1
support was found to be intact incorporation of nickel oxide. The infrared spectra showed that the
tetrahedral titanium in the TS-1 is still remained after impregnation with nickel oxide. The
hydrophilicity of the modified samples increased as a function of the amount of nickel oxide loading, on
contrary with XRD peak intensity.
Key words: Hydrophobicity, NiO/TS-1, Microporous material
Introduction
Hydroxylation of Phenol to hydroquinone and
catechol is an important reaction for many industrial
applications, such as: photographic film developer,
antioxidant, polymerization inhibitor, medicines,
perfumes, and etc [1]. Dihydroxybenzenes are
largely used today as intermediate chemicals. They
are produced by decomposition of diisopropyl
benzenes hydroperoxides or by hydroxylation of
phenol in strong acid. Hydroquinone (pdihydroxybenzene) was also produced by the
oxidation of aniline using manganese dioxide and
sulfuric acids. This was then followed by reduction
using typically Fe/HCl [2]. This is homogenous
catalytic process, the disadvantage found in case of
homogeneous catalytic process is being highly
expensive and hydroxylation of phenol gives very
low para to ortho ratio [3]. But the use
heterogeneous catalyst is a promising alternative to
over come this problem. So many works have been
done to enhance the production of hydroquinone and
cathecol due to importance in industrial. Titanium
silicalite molecular-sieves (TS-1) for hydroxylation
of phenol with hydrogen peroxide as the oxidant was
discovered in 1983 by Taramasso et al. and since
then it has gradually been acknowledged as one
Proceeding Book
milestone in heterogeneous catalysis. This reaction is

environmentally friendly because only produce water
as by-product. In addition, hydrogen peroxide is a
stable reagent with high active oxygen [4]. One of
the advantages of TS-1 is higher para selectivity,
which is attributed to the shape selectivity of the
catalyst. Another advantage of this catalyst is the
higher phenol conversion and the low amount of tar
formation [5]. The conversion of hydroxylation of
phenol with hydrogen peroxide catalyzed by TS-1
obtained 97% [6].
From the unique properties, TS-1 has
hydrophobic nature. The hydrophobicity nature of
TS-1 can be decreased by incorporation of metal
oxide. It has been reported that the presence of metal
oxide even in very small amount can be increased the
catalytic activity due to hydrogen peroxide with TS1 formed Ti-peroxo easily. Though hydrophilicity
increases, acid sites also increases. Acid sites
(Brnsted and Lewis) can be found in some
transition metals such as metal oxide of V2O5,
Nb2O5, MoO3, WO3, Re2O7, NiO, ZnO, Fe2O3,
Cr2O3, dan Cr2O3/Al2O3 [7]. The use of
heterogeneous catalysts is an alternative for
oxidation reactions due to more effective than
homogeneous catalysts. The other heterogeneous
catalysts for hydroxylation phenol are CuOMCM
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TS-1 was prepared according to a procedure

described in the literature [15] with slight
modification, using tetraethyl orthosilicates TEOS
(Merck 98%), tetraethyl orthotitanate TEOT
(Merck
95%)
in
isopropyl
alcohol,
tetrapropylammonium
hydroxide (Merck 20%
TPAOH in water), and distilled water. The gel was
charged into 300 ml autoclave and heated at 175 oC
under static condition. The material was recovered
after 4 days by centrifugation and washed with
excess distilled water. A white powder was
obtained after drying in air at 100 oC overnight. The
calcinations of sample to remove the template was
carried out in air at 550 oC for 5 hour with
temperature rate 1 omin-1.
Sample NiO/TS-1, TS-1 loaded with nickel
oxide (0.5; 1; 2; 4) were prepared by impregnation
technique using Ni(NO3)2 as a precursor. About
0.0126 g of Ni(NO3)2 was dissolved in distilled
water to obtain the desired metal loading and
required quantity of pre-dried of TS-1 was
immediately added to clear solution with stirring.
The mixture was stirred at room temperature for 3
hour. The solid was recovered by evaporating the
distilled water at 80 oC. The solid was then dried at
100 oC for 24 hour. Then solid was calcined at 500
o
C for 5 hour with temperature rate 1 omin-1. The
method and compositions of the samples are listed
in Table 1.
48 [8], V2O5/Nd2O3 [9], CuVSB5 [10],

molibdovanadofosfor/ZrO2 [3], FeHMS [11].
The increased of loading nickel oxide ca be
increased catalytic activity for dimerization and
isomerization of olefins [12]. It has been reported
that the impregnation of MoO3 on TS-1 can be
increased hydrophilicity and acid sites, therefore, its
catalytic activity for hydroxylation of phenol also
increased [13]. The conversion of phenol on
MoO3/TS-1 catalyst is higher than TS-1 catalyst was
reported [14].
In this paper, nickel oxide has been loaded on
the surface of TS-1 to introduce acidity.
Commonly, in the TS-1 structure, titanium was
initially assumed to occupy a substitute position in
the zeolite framework, since XRD measurements
indicated that unit cell volume increases linearly
with the Ti content, in good agreement with the
isomorphous substitution of Ti for Si at tetrahedral
framework sites. However, the local environment
of Ti in TS-1 can studied using several techniques
such as FTIR. The hydrophobicity of TS-1 can
studied using hydrophobicity tests using the
mixture of xylene and water.
Table 1: The sample code and preparation method

Sample
The code of
sample
NiO/(NiO+TS-1),%
Method
Titanium silicalite
(TS-1)
TS-1
1 *(gel)
hydrothermal
0.5% NiO/TS-1
0.5NiO/TS-1
0.5
Impregnation- hydrothermal
1% NiO/TS-1
1NiO/TS-1
2% NiO/TS-1
2NiO/TS-1
4% NiO/TS-1
4NiO/TS-1
100
calcination
NiO
NiO
* (%Ti) = Ti/(Ti+Si)
All molecular sieves were characterized by

powder X-ray diffraction (XRD) for identification
of the crystalline phases in the catalysts using
diffractometer with the Cu K ( = 1.5405 )
radiation as the diffracted monochromatic beam at
40 kV dan 40 mA. Typically, powder sample were
ground and spread into a sample holder and then
analyzed. The pattern was scanned in the 2 range
of 550o at step 0.020o and step time 1 second.
Infrared (IR) spectra of samples were collected on a
Perkin Elmer Fourier Transform Infrared (FTIR)
spectrophotometer, with a spectral were recorded in
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the region of 1400 400 cm-1. Hydrophobicity test

were determined by the mixture of xylene and
water, which do not mix each other. Xylene and
water of the same volume are added into a test tube
to form a stable phase interface, as shown in figure
1. TS-1 and NiO/TS-1 samples were dispersed in
the xylene-water system and stirred. After the
mixture has stabilized, hydrophobic characteristics
can be qualitatively evaluated by inspecting the
state of the floating/sinking of samples pass the
phase interface and sinking of samples at the
interface. The criteria of hydrophobic index is as
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follows: (1) hydrophilic: samples pass the phase

interface and sink into water quickly and
completely; (2) hydrophilic: samples pass the phase
interface and sink into water not so quickly; (3)
hydrophilic: samples float at first on the phase
interface and then sink into water slowly and
completely; (4) partially hydrophilic: samples float
at first on the phase interface and then some

particles sink into water completely; (5) partially
hydrophobic: samples float on the phase interface.
After mixing a long time, some particles still float
on the phase interface; and (6) completely
hydrophobic: samples float on the phase interface
even with vigorous mixing for along time [16].
Xylene
Interface
Water
Figure 1. Testing of hydrophobic nature of sample

X-ray Diffraction (XRD)
The XRD pattern of the samples are shown
Figure 2, while the phase containing sample are
tabulated in Table 2. The XRD pattern of TS-1 and
NiO/TS-1 sample indicated that the sample
contained framework structures of the MFI type
zeolite. The XRD pattern showed the framework
structures of the MFI at 2 = 8.00; 8.88; 23.12;
23.18; 23.44; 23.74. The peak at 2 = 24.45
indicated a changing of a monoclinic symmetry
(silicalite) to an orthorhombic symmetry (titanium
silicalite, TS-1) [17]. For sample NiO/TS-1, the
structure of TS-1 is not strongly affected by the
presence of impregnated nickel oxide. The XRD
pattern showed that no diffraction line assigned for
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crystalline phase of the nickel oxide were

investigated. This indicated that nickel was well
dispersed on the TS-1. The peak intensity of
NiO/TS-1 with various loading is drastically
decreased as addition of nickel oxide increased. It is
suggested that nickel is either located on the surface
of TS-1 or covering the surface of TS-1.
Table 2 The crystallinity of TS-1 and NiO/TS-1
samples
Intensity at
Phase
Code sample
2 = 23.18, a.u
TS-1
3083
MFI
0,5 NiO/TS-1
3035
MFI
1 NiO/TS-1
2720
MFI
2 NiO/TS-1
2598
MFI
4 NiO/TS-1
2563
MFI
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4NiO/TS-1
2NiO/TS-1
Intensity, a.u.
1NiO/TS-1
0.5NiO/TS-1
TS-1
NiO
5.00
15.00
25.00
35.00
45.00
2 theta, degree
Figure 2 XRD pattern of the NiO, TS-1, and XNiO/TS-1 samples
Fourier Transform Infrared (FTIR) Spectroscopy

The infrared spectra of the samples in the
lattice vibration region between 1400 and 400 cm-1
are depicted in figure 3. Sample TS-1 and
XNiO/TS-1 showed similar bands. According to
Flanigen [18], the absorption bands at around 1100,
800, and 450 cm-1 were three lattice modes
associated with internal linkages in tetrahedral SiO4
and are insensitive to structure changes. The
absorption bands at about 1225 and 547 cm-1 are
characteristic of MFI type zeolite associated with
the particular structural assembly of the tetrahedral
and are sensitive to structure changes. It is already
known that the infrared spectrum of titanium
silicalite, TS-1 is characterized by an absorption
band at around 960 cm-1. However, the vibrational
modes at around this frequency may be the result of
several contributions i.e. the asymmetric stretching
modes of Si-O-Ti linkages, terminal Si-O stretching
of SiOH-(HO)Ti defective sites and titanyl
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[Ti=O] vibrations [19]. Our TS-1 sample shows a

weak band at 970 cm-1. This band can be attributed
to the titanium in the framework and with addition
NiO
of nickel oxide onto TS-1 by impregnation still
-1
show band at 970 cm . It included that TS-1 and
NiO/TS-1 sample contains Si-O-Ti connections.
In addition, a small band at around 970
cm-1 assigned to the titanium ions in the tetrahedral
structure is still present after impregnation of nickel
(NiO/TS-1). No additional band after impregnation
of nickel into the TS-1 can be observed. This
finding shows that impregnation of nickel has not
effected the MFI structure of TS-1 significantly.
Meanwhile, infrared spectroscopy technique cannot
detect the presence of nickel oxide in the sample
NiO/TS-1, due to addition nickel oxide into TS-1 is
low. However, the frequency of bands decreased as
the amount of loading nickel oxide in the
investigated samples increased.
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January 24, 2009
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1100
970
550
800
459
4NiO/TS-1
2NiO/TS-1
1NiO/TS-1
Transmittance, %
0 5NiO/TS-1
TS-1
NiO
1400
1200
1000
800
-1
Wave number cm
600
400
Figure 3. Spectra FTIR of the TS-1, XNiO/TS-1 samples
Hydrophobicity Tests
The results of hydrophobic tests are shown in
the Table 3. From Table 3, it can be seen that TS-1
sample is strongly hydrophobic, while NiO/TS-1
samples are more hydrophilic than TS-1. The result
of hydrophobicity tests with the criterion of
hydrophobic index are (1) until (6) [16]. The
purpose of this observation of time is to compare

hydrophilicity
among
the
samples.
The
incorporation of nickel oxide can be increased the
hydrophilic nature of TS-1. The hydrophilicity of
NiO/TS-1 samples increased as a function of nickel
oxide loading, as shown in Table 3.
Table 3. The results of hydrophobicity tests of all samples
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January 24, 2009
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No.
Sample
1.
2.
3.
4.
5.
TS-1
0.5NiO/TS-1
1NiO/TS-1
2NiO/TS-1
4NiO/TS-1
Criterion of
hydrophobic index
5
5
5
5
3
Among all samples, 4NiO/TS-1 sample showed the

faster drop than the other samples, while TS-1 is
the lowest. It is indicated that TS-1 has
hydrophobic character with hydrophobic index 5.
While 4NiO/TS-1 sample showed strongly
hydrophilic than other samples (Table 3). 4NiO/TS1 has hydrophilic character with hydrophobic index
3, when samples float at first on the phase interface
and then sink into water slowly and completely, as
shown in Figure 4e. It indicated the incorporation
of nickel oxide can be increased the hydrophilicity
of TS-1 and can effect of catalytic activity. Besides
Time
2 minutes 31 seconds
1 minutes 26 seconds
1 minutes 6 seconds
1 minutes 1 seconds
50 seconds
that, with the incorporation of nickel oxide can be

increased Lewis acid site. Lewis acid site can be
effect hydrophilicity of TS-1 because can be accept
free electron pairs from water. This is will be
studied further. All samples with hydrophobic
index 5, before stirring float on the interface, after
stirring and keep on overnight some particles still
float on the interface, as shown in Figure 4 and 5.
But sample with hydrophobic index 3, there is no
particles float at the interface before and after
stirring.
Figure 4: Sample TS-1 (a) and XNiO/TS-1 (X = 0.5, 1, 2, and 4) (b-d) in the water-xylene before stirring.
a
0.5NiO/TS-1
1NiO/TS-1
2NiO/TS-1
4NiO/TS-1
Figure 5: Sample TS-1 (a) and XNiO/TS-1 (X = 0.5, 1, 2, and 4) (b-d) in the water-xylene after stirring.
Conclusion
Proceeding Book
NiO/TS-1
catalysts
were
successfully
synthesized by impregnation of nickel oxide on the
surface of TS-1. X-ray diffraction indicated that all
499

January 24, 2009
ISBN : 978 979 19201 0 0
the samples had the MFI crystalline structure. The

MFI crystalline structure was not changed with the
loading of nickel oxide. Infrared spectroscopy
showed band at around 960 cm-1, attributed to the
titanium in the framework and spectra was still
remained with the loading of nickel oxide. The
increasing of catalyst hydrophobicity depended on
the loading amount of nickel oxide.
Acknowledgements
We gratefully acknowledge funding from the
Directorate General of Higher Education,
Indonesia, under Hibah grant.
References
[1] Schudel, P., Mayer, H., Isler, O., Sebrell, W. H.,
Harris, R. S., (1972), Academic Press: New
York, 5: 165 317.
[2] Corma, A and Garcia, H, (2002), Lewis Acid as
Catalysts in Oxidation Reactions: From
Homogeneous to Heterogeneous Systems,
Chem. Rev.
[3] Parida, K. M., Mallick, S., (2008),
Hydroxylation
of
Phenol
Over
Molybdovanadophosphoric Acid Modified
Zirconia, J. Mol. Catal. A: Chemical, 279:
104-111.
[4] Smith, G. V., Notheisz, F., (1999),
Heterogenous
Catalysis
in
Organic
Chemistry, Elsevier.
[5] Bellussi, G., Millini, R., Previde, M. E., Perego,
G., (1992), Framework Composition of
Titanium Silicate-1, J. Catal., Vol. 137,
Hal. 497-503.
[6] Bianchi, Daniele, Aloisio, D. R., Bortolo, R.,
Ricci, M., (2007), Oxidation of Mono- and
Bicyclic Aromatic Compounds with
Hydrogen Peroxide Catalyzed by Titanium
Silicates TS-1 and TS-1B, Appl. Catal. A:
General, 327: 295-299.
[7] Kung, H.H, (1989), Transition Metal Oxides:
Surface Chemistry and Catalysis, Study
Surface Science and Catalyst, Elsevier,
New York. 45.
[8] Lou, L., and Liu, S. (2005), CuO-Containing
MCM-48 as Catalysts for Phenol
Hydroxylation, Catal. Commun., 6:762765.
[9] Shylesh, S., Radhika, T., Sreeja, K. R.,
Sugunan,
S.,
(2005),
Synthesis,
Characterization and catalytic activity of
Nd2O3 supported V2O5 catalysts, J. Mol.
Catal. A: Chemical, 236: 253-259.
[10] Jiang, Y., Gao, Q., (2007), Preparation of
Cu2+ - VSB-5 and Their Catalytic Properties
Proceeding Book
on Hydroxylation of Phenol, Mater. Lett.,

61: 2212-2216.
[11] Liu, H., Lu, G., Guo, Y., Guo, Y., Wang, J.,
(2008), Study on The Synthesis and The
Catalytic Properties of Fe-HMS Materials in
The Hydroxylation of Phenol, Micro.
Meso. Mater., 108: 56-64.
[12] Rack, J. Sohn, (2002), Catalytic Activities of
Nickel-Containing Catalysts for Ethylene
Dimerization and Butene Isomerization and
Their Relationship to Acidic Properties,
Catal. Today, 73:197-209.
[13] Liu, Y., Ma, X., Wang, S., Gong, J. (2007),
The Nature of Surface Acidity and
Reactivity of MoO3/SiO2 and MoO3/TiO2SiO2 for Transesterification of Dimethyl
Oxalate with Phenol: A Comparative
Investigation,
Appl.
Catal.
B:
Environmental, 77: 125-134.
[14] Indrayani, Suci, (2008), Aktvitas Katalitik
menggunakan H2O2, Tesis, Institut Sepuluh
November, Surabaya.
[15] Taramasso, M., Perego, G., Notari, B. (1983),
Preparation of Porous Crystalline Synthetic
Material Comprised of Silicon and Titanium
Oxides, (U. S. Patents No. 4,410,501).
Organic modification of ultrafine particles
using carbon dioxide as the solvent, J.
Powder Technology, 139: 148-155.
[17] Li, Y.G., Lee, Y.M., Porter, J.F. (2002), The
Synthesis and Characterization of Titanium
Silicalite-1, Kluwer Academic Publishers,.
0022-2461.
[18] Flanigen. E. M. (1976), Structural Analysis
By Infrared Spectroscopy. In: Rabo, J.
A.ed. Zeolite chemistry and catalysis, ACS
Monograph 171: 80-117.
[19] Prasetyoko, D., Ramli, Z., Endud, S., Nur, H.
(2005a), Preparation and Characterization
of Bifunctional Oxidative and Acidic
Catalysts Nb2O5/TS-1 for Synthesis of
Diols. Mater. Chem. and Phys., Vol. 93,
hal. 443-449.
500

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Coal Fly Ash Geopolymer:

Study of SiO2/Al2O3 Mol Ratios and the Resulted Geopolymer Properties
Ella Kusumastuti 1, Hamzah Fansuri 2, Lukman Atmaja 3*,
1
Chemistry Department, Sepuluh Nopember Institute of Technology, Surabaya

Chemistry Department, Sepuluh Nopember Institute of Technology, Surabaya
*
Corresponding author : lukman_at@chem.its.ac.id
2, 3
Abstract
The effect of SiO2/Al2O3 mol ratio with the contribution of each SiO2 and Al2O3 in the reaction
mixture to the chemical and mechanical properties of the geopolymer product has ben investigated.
Type C of fly ash from Cilacap Power Plant was used as the based material which had initial mol ratio
SiO2/Al2O3=4.32. Two series of variation SiO2/Al2O3 were made by varying the amount of soluble
additives (Na2SiO3 and Al(OH)3) added to the initial reaction mixture (fly ash, Na2SiO3, NaOH, and
H2O). All conditions have been done at constant consistency.
The results showed that the addition of aluminate species at constant silicate and the reduction of
NaOH molarity increase the setting time due to more Al(OH)3(H2O) complex species was available to
inhibited polycondensation reaction. The optimum compressive strength was achieved at mol ratio of
SiO2/Al2O3=3.0 for Al2O3 series and SiO2/Al2O3=5.0 for of SiO2 series. Phase development showed
that the greater SiO2/Al2O3 mol ratio, the greater formation of amorf homogenous phase and lead to
reach optimum SiO2/Al2O3 mol ratio. FTIR study showed that the greater SiO2/Al2O3 mol ratio, the
greater the wave number of vibration meaning both the increasing of chain length Si-O-Al or Si-O-Si
and the vibration energy. It also revealed that there were more formation of gel aluminosilicate in
geopolimerisation and that the chemical bond of Si-O-Al or Si-O-Si getting strong at optimum
SiO2/Al2O3 mol ratio. Grain structure appeared at low SiO2/Al2O3 causing a lower strength, while
homogenous geopolymer matrix appeared at optimum SiO2/Al2O3 mol ratio cauisng to a higher
strength. Unreacted fly ash and residual reactant appeared at high SiO2/Al2O3 mol ratio and lead to a
lower strength.
Keywords: geopolymer, coal fly ash, aluminosilicates, SiO2/Al2O3
Introduction
Efforts for reducing the world cement consumption
have been developed by synthesing material that
has cementitious properties and potential to
partially replaced conctrete. Davidovits, a scientist
in polymer, in 1978 for the first time developed
aluminosilicate
inorganic
polymer
called
geopolymer (Davidovits, 1994). Geopolymer which
has general formula nM2OAl2O3 xSiO2 yH2O was
obtained from polycondensation reaction of
pozzolanic materials or alumonosilicate minerals
with alkali silicate solution (Davidovits, 1991).
This relatively new material has a similar
cementitious properties to concrete.
Fly ash, by-product of coal-based industry, has
pozzolanic properties as its major content are
reactive silica and alumina. Thus, it is a good
starting materials to synthesize geopolymer.
Pozzolanic properties describes the reactivity of
silica and alumina which took a part in the
formation of Si-O-Al chains in geopolymer.
One of major parameters in the initial mixture of
the starting material, in the case of fly ash, is the
quantity of the essential compounds involved in the
Proceeding Book
formation of geopolymer chains. SiO2 and Al2O3

are the major oxides besides the other oxides which
have an important role in the formation of Si-O-Al
chains in geopolymer. The dissolution of silica and
alumina in the surface of fly ash was determined by
the chemical composition of fly ash itself (Rizain,
2008). In the high alkali condition, Al2O3
solubilities were greater than that of SiO2 (Swaddle,
2001). In the condition of more reactive
SiO2/Al2O3, there would be a different contribution
of silica and alumina, i.e., alumina is responsible
for initial properties while silica is for final
properties.
This research was objected for studying the effect
of SiO2/Al2O3 moles ratio having contribution of
each SiO2 and Al2O3 in the starting material to the
chemical and mechanical properties of the
geopolymer product such as setting time,
compressive strength, phase development, the
changing of chemical bond and microstructure.
Materials and Method

Fly ash from Cilacap Power Plant was used as the
based material, and NaOH, H2O, sodium silicate
501

January 24, 2009
ISBN : 978 979 19201 0 0
and aluminium hidroxide were used as additive

(added aluminate species). Some standard
laboratory tools were used to mix and mold the
geopolimer matrixs. X-Ray Fluorescence (XRF)
was used for the determination of fly ash
composition, while the characterisations of
geopolymer such as setting time, compressive
srength and phase development used a Vicat Needle
Apparatus, Universal Testing Machine and X-Ray
Diffraction (XRD), respectively. Scanning Electron
Microscopy (SEM) was used to investigate the
morphology and Fourier Transform Infra Red
(FTIR) to investigate chemical bond of the resulted
geopolymer.
At first, geopolymer synthesis has been carried out
by mixing the fly ash with activator (NaOH
solution). The initial mixing was done by hands for
2 minutes then by mixer for 5 minutes so the
mixture was really homogenous (van Deventer,
2000 and van Jaarsveld, 2002). The mixture then
poured into plastic cilinder mold with 1.5 cm in
diametre and 3 cm in high (Bakharev, 2005 and
Andini, 2008). Vibration has been done for about
15 minutes to remove air bubble in paste so it was
be more dense (Duxson, 2005). The result of
moulding process was let in the room temperature
for 2 hours until it could be released from its
mould. It then was sealed/wrapped with plastics to
avoid loosing water quickly which could the pellet
cracked. Pellets then cured at 60C for 24 hours in
the oven (Chindaprasirt, 2007 and Aly, 2008) to
maximise the reaction of geopolymerisation.
The SiO2/Al2O3 mol ratios were made by varying
the amount of soluble additives (Na2SiO3 and
Al(OH)3, respectively) that added to the initial
reaction mixture (fly ash, Na2SiO3, NaOH, and
H2O). Two series of variations were used. The first
was achieved by varying Al2O3 content at constant
SiO2 and the other was achied by varying SiO2
content at constant Al2O3. The amount of Na2O in
all variations was kept constant. Water was added
to achieve the same mixture consistency in all
variations.
The total moles in every composition were
presented below :
Table 1 The Total Moles in Variation of Al2O3 at
Constant SiO2
Total Moles
SiO2
Al2O3
Na2O
0.217
0.217
0.217
0.217
0.217
0.217
0.434
0.217
0.145
0.109
0.087
0.072
0.113
0.113
0.113
0.113
0.113
0.113
Proceeding Book
SiO2/Al2O3
0.5
1.0
1.5
2.0
2.5
3.0
0.217
0.217
0.217
0.217
0.217
0.062
0.054
0.048
0.043
0.043
0.113
0.113
0.113
0.113
0.113
3.5
4.0
4.5
5.0
5.064
Table 2 The Total Moles in Variation of SiO2 at

Constant Al2O3
Total Moles
SiO2
Al2O3
Na2O
0.021
0.043
0.064
0.086
0.107
0.129
0.150
0.171
0.193
0.214
0.217
0.043
0.043
0.043
0.043
0.043
0.043
0.043
0.043
0.043
0.043
0.043
0.113
0.113
0.113
0.113
0.113
0.113
0.113
0.113
0.113
0.113
0.113
SiO2/Al2O3
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.064
The gepolymer pellets then were characterized for

studying the chemical properties after cured for 28
days (Hardjito, 2004). The mechanical properties
were determined after 1 and 28 days.

Fly ash Characterization
The composition of fly ash from Cilacap Power
Plant is presented in Table 3. It can be seen that the
major oxides of the fly ash were SiO2, Al2O3, CaO
and Fe2O3. This fact lead to catagorising the fly ash
as class C.
Phase analysis by XRD showed that the phase
majority was quartz (SiO2) and mullite (3Al2O3
xSiO2) and albite (NaAlSi3O8)in minor amount.
Most of them were amorf and it was signed by the
present of hump at 2 20 up to 30. Amorf phase
in fly ash showed reactivity of silica and alumina in
fly ah, because only amorf phase could dissolve in
high alkali solution (Duxson et al, 2007).
Table 3 The Composition of Fly Ash
Oxide
% Mass Oxide
SiO2
31,50
Al2O3
12,40
CaO
21,40
Fe2O3
22,50
K2O
0,75
MgO
7,87
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Na2O
P2O5
SO3
TiO2
MnO
BaO
SrO
LOI
Figure 2 Final Setting Time of SiO2/Al2O3 Mol

Ratios
0,27
0,12
1,06
0,76
0,27
0,24
0,09
0,49
200
150
intensity
M
100
Q
50
QQ Q Q
10
20
30
40
50
60
70
80
2 tetha
Figure 1 X-Ray Diffraction Spectra of Fly Ash

Setting Time and Strength Development
Setting Time by Vicat Needle Apparatus
Geopolimer paste setting time is defined as time
needed for transport, placing and compaction
process (Teixeira-Pinto, 2002). Terms transport
and placing describe the transportation process of
dissolved species (Si and Al) from particle surface
of fly ash into interparticle spaces, while the term
compaction describes the polycondensation process
of the the species to form aluminosilicate three
dimensional structure.
Determination of geopolymer paste setting time by
Vicat Needle Apparatus presented in Figure 2
below :
Al(OH)3 + OH Al(OH)4 ........................

Al(OH)3 + OH + H2O [Al(OH)3(H2O)]0
SiO2 + OH- [SiO2(H2O)]2 .......................
SiO2 + OH + H2O [SiO(OH)3] .............
(4.1)
(4.2)
(4.3)
(4.4)
It could be understood that in very high alkaline

condition, Al(OH)4 and [SiO2(H2O)]2 play more
important role than [Al(OH)3(H2O)]0 and
[SiO(OH)3] so that the policondensation reactions
of the geopolymerisation process was also quicker
that that of the low alkaline condition. The greater
addition of Al(OH)3, the lower SiO2/Al2O3 mol
ratios, the more [Al(OH)3(H2O)]0 available, the
more difficult polycondensation reaction to happen,
and so the longer the setting time.
Compressive Strength by Universal Testing
Machine
Final Setting Time of SiO2/Al2O3 Mol Ratios
200
The mol ratios of SiO2/Al2O3 increase as the

addition of Al3+ species from Al(OH)3 decrease
from a sample to another (Table 1). Figure 2 shows
that the greater SiO2/Al2O3 mol ratios, the shorter
the setting time. This behaviour could be explained
by the role of aluminium hydroxide. The Al(OH)3
additions to the system of the geopolymerisation
process would cause the setting time of geopolymer
was stretched from a sample to another. Further
explanation could arise from a fact that in this
composition the NaOH molarities increased with
increasing SiO2/Al2O3 mol ratios and that of the fly
ash fraction did, too. Both NaOH molarities and the
solid fraction had been reported to have significant
effects to setting time (Kamhangrittirong et al,
2006) due to the need of water to reach the same
consistency was different. The greater SiO2/Al2O3
mol ratios, the less needed water and this mean the
greater NaOH molarity.
In the strong alkaline solution with high pH where
NaOH molarity is high, the formation of aluminates
Al(OH)4 is preferred to have [Al(OH)3(H2O)]0
form and [SiO2(OH)2]2- is preferred to have
[SiO(OH)3]- form (Weng, 2005) following the
equations below :
Final Setting Time (minutes)
180
To study strength development of SiO2/Al2O3 mol

ratios, measurements of compressive sterngth were
carried out at different age, 1 day for initial strength
and 28 days for final strength. Compressive
strength development of geopolymer with variation
of SiO2/Al2O3 mol ratios is presented in Table 4.
160
140
120
100
80
60
40
20
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
SiO2/Al2O3 Moles Ratio

Mol Variation of Al2O3 at Constant SiO2
Mol Variation of SiO2 at Constant Al2O3
Proceeding Book
503

January 24, 2009
ISBN : 978 979 19201 0 0
Table 4 Compressive Strength Development of Geopolymer with Variation of SiO2/Al2O3 Mol Ratios
Al2O3 Variation
SiO2 Variation
Strength Increase
SiO2/Al2O3
Initial
Final
Initial
Final
Al2O3
SiO2
Mol Ratios
Strength
Strength
Strength
Strength
Variation Variation
(MPa)
(MPa)
(MPa)
(MPa)
0.5
0.60
1.51
2.50
1.0
30.92
52.04
1.68
1.5
31.87
64.20
0.66
0.85
2.01
1.29
2.0
35.64
66.75
1.51
11.13
1.87
7.38
2.5
39.41
78.06
2.04
21.13
1.98
10.36
3.0
58.92
91.07
11.32
31.70
1.55
2.80
3.5
48.08
85.79
13.76
34.90
1.78
2.54
4.0
40.73
68.08
27.72
44.69
1.67
1.61
4.5
43.94
56.71
52.04
54.30
1.29
1.04
5.0
54.49
74.67
47.18
70.90
1.37
1.50
The Average of Strength Increase
1.77
3.56
Compressive Strength (MPa)
Compressive Strength of SiO2/Al2O3 Mol Ratios

100.00
90.00
80.00
70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
SiO2/Al2O3 Mol Ratios

Initial StrengthInitial
of AlStrength
inal Strength
of Al2O3
Al2O3 Variatio
on Al2O3 Variation FFinal
Strength on
Variationn
2O3 Variation
Strength
on SiO2 Variation
Initial StrengthInitial
of SiO
2 Variation
Final Strength
Strength on
Final
of SiO2
SiO2 Variation
Variation
Figure 3 Compressive Strength Development of Geopolymer with Variation of SiO2/Al2O3 Mol Ratios
In the variation of Al2O3 moles at constant SiO2,
there were similar trends in both initial and final
compressive strength. Figure 3 exhibited that the
greater SiO2/Al2O3 mol ratios, the greater
compressive strength and the optimum value was
reached at SiO2/Al2O3 = 3.0, i.e., 58.92 Mpa and
91.07 MPa for 1 and 28 days, respectively. The
compressive strength decreased at SiO2/Al2O3 = 3.5
and it decreased with increasing SiO2/Al2O3 mol
ratios. The average final strength increase was 1.77
times more than the initial strength. These
important data could be correlated with the setting
time data previously presented in Fig.2. Setting
time at SiO2/Al2O3 3 was low and it decreased
with increasing SiO2/Al2O3 mol ratios. Setting time
at SiO2/Al2O3 < 3 were increased significantly with
decreasing SiO2/Al2O3 mol ratios.
Proceeding Book
In the variation of SiO2 moles at constant Al2O3, the

trend in both initial and final compressive strengths
was different. The initial stength increased with
increasing SiO2/Al2O3 mol ratios, and reached
maximum value at SiO2/Al2O3 = 4.5, i.e., 52.04
MPa, while final strength reached maximum valua
at SiO2/Al2O3 = 5.0, i.e., 70.90 MPa. The average
final strength increase was 3.56 times more than the
initial. The addition of SiO2 moles clearly
influences the development of the compressive
strength.
The average increasing final strength on SiO2
variation was greater than that on Al2O3 variation.
One then could concluded that the final strength
development was influenced mainly by SiO2 mol
addition. However, all of strengths in Al2O3
variation was greater than all of strengths in SiO2
504

January 24, 2009
ISBN : 978 979 19201 0 0
variation. It could be explained that SiO2/Na2O

mol ratio in Al2O3 variation was greater than in
SiO2 variation. Na2O species could reduce the
strength of geopolymer because it would form
Na2CO3 if it reacted with CO2 in the air. Density of
Na2CO3 was also low also and could reduce the
strength of geopolymer.
X-Ray Diffraction spectroscopy was used to

determine the phase mineralogy of geopolymer
with variation of SiO2/Al2O3 moles. It was
conducted on geopolymer sample aged of 28 days
to ensure that the geopolymerisation process was
stable.
For the variation of Al2O3 moles, the spectra is
presented in Figure 4 below :
Phase Development by XRD
Q
G
G Q
G G
Q
20
Q
Q
Q
QQ
Q
SiO2/Al2O3=5.0
Q
M MM
Q
M MM
Q
GK Q G
QQ
Q
SiO2/Al2O3=3.0
Q Q GQ
SiO2/Al2O3=2.0
G
QG
10
SiO2/Al2O3=5.06
MaM M
Q
Q
intensity
Q
Ma M M
30
G
G
KG G G
G G
G
Q Q
Q
QQ
40
50
60
SiO2/Al2O3=0.5
70
80
2tetha
Figure 4 X-Ray Diffraction Spectra of Geopolymer with Variation of Al2O3 Moles

Q=quartz (SiO2), M=mullite (3Al2O3.2SiO2), G=gibbsite (Al(OH)3),
Ma=magnetite (FeFe2O4), K=kaolinite (Al2Si2O5(OH)4)
The formation of geopolymer was signalled by the
shift of 2=20-30 in fly ash into 2=25-35 in
geopolymer. From spectra in Figure 4 it could be
seen that at low SiO2/Al2O3 mol ratio, there was
more crystaline phase than at high SiO2/Al2O3 mol
ratio. It was very clear that at SiO2/Al2O3 = 0.5,
most of all phase were crystaline with the main
minerals are gybbsite and the minor minerals are
quartz. It should be noted that SiO2/Al2O3 = 0.5 was
the larges of Al(OH)3 addition. The phase of
gibbsite then decreased with increasing SiO2/Al2O3
mol ratio because the addition of Al2O3 mol was
also decreased. On the other hand, quartz phase
increased with increasing SiO2/Al2O3 mol ratio.
Some minor minerals appeared because of the
Proceeding Book
heterogenousity of fly ash component such as

magnetite and kaolinite while the major minerals
such as quartz and mullite came from both alumina
and silika species. All spectra in Figure 4 showed
that the most homogenous phase was found at
SiO2/Al2O3=3.0 because it only contained quartz
and mullite. This data could explain the sample
with SiO2/Al2O3=3.0 had the highest strength.
When a materials contain more amorphous phase,
its strength would have a higher strength. However,
SiO2/Al2O3=0.5 samples had the lowest value in
strength because it contain very crystaline phase.
Amorphous phase had more rigid structure than
crystaline phase which had more brittle structure.
505

January 24, 2009
ISBN : 978 979 19201 0 0
Q
MaMM
Q
K
Q
SiO2/Al2O3=5.06
Q
Q
MaM M Q
KQ Q
SiO2/Al2O3=5.0
intensity
Q
S
Q
Q G M M Q G Q Q KQ
Q
Q
Q G S MM QQ G
Q
Q
S Ma
Q Q
Q Q
Q
G M Q G Q QG G
Q
Ma
Q
S
0
10
20
30
40
50
60
Q SiO /Al O =3.5

2
2 3
SiO2/Al2O3=2.5
SiO2/Al2O3=1.5
70
80
2tetha
Figure 5 X-Ray Diffraction Spectra of Geopolymer with Variation of SiO2 Moles

Q=quartz (SiO2), M=mullite (3Al2O3.2SiO2), G=gibbsite (Al(OH)3),
Ma=magnetite (FeFe2O4), K=kaolinite (Al2Si2O5(OH)4),
S= sodalite (Al6Na8(SiO4).6Cl2)
From spectra in Figure 5 shows the phase
development of SiO2 variation. It can be seen that
the minerals phase were more heterogenous than
the samples coming from Al2O3 variation. The
greater SiO2/Al2O3 mol ratios, the more
homogenous and more amorf its mineral. Some
minor minerals appeared because of the
heterogenous of fly ash component such as
magnetite and kaolinite while the major minerals
such as quartz and mullite came from both alumina
and silika species. Small zeolite phase such as
sodalite appeared in low SiO2/Al2O3 mol ratios, that
were SiO2/Al2O3=1.5; 2.5 and 3.5. From all spectra
in Fig. 5, it could be seen that SiO2/Al2O3 = 5.0 was
the most homogenous phase so it supported that
final strength at SiO2/Al2O3 = 5.0 was the highest.
SiO2/Al2O3 = 1.5 had heterogenous phase with the
greatest gibbsite phase leading to the lowest final
strength value.
Chemical Bond Development by FTIR
FTIR spectroscopy was used to investigate the
chemical bond in geopolymer using the variation of
SiO2/Al2O3 mol ratios. This study is based on the
vibration of molecules as a result of its interaction
with the infrared waves. The change of resulted
vibration spectra was investigated.
The main characteristic of vibration spectra
appeared as a sign that Si-O-Al chain in
Proceeding Book
geopolymer has been formed. Vibration spectra at

wave number 1090-990 cm-1 signed asymetric
stretching vibration of Si-O-Al or Si-O-Si while
vibration at 750-550 cm-1 signed symetric
stretching vibration of Si-O-Al or Si-O-Si.
Vibration at 470-450 cm-1signed the bending
vibration of Si-O-Al or Si-O-Si and vibration at
about 800cm-1 signed AlO4 vibration (Bakharev,
2005).
FTIR spectra of geopolymer with variation of
Al2O3 moles and variation SiO2 moles were
presented at Figure 6 and Figure 7 below. The
investigation was conducted by comparing each of
the spectra. It shows that the greater SiO2/Al2O3
mol ratios, the higher its intensity. Increasing
intensity meant increasing the chain length of Si-OAl or Si-O-Si and it signed that there were more
formation
of
gel
aluminosilicate
in
geopolimerisation. It also showed that the greater
SiO2/Al2O3 mol ratios, the greater the wave
number. Increasing wave number meant increasing
vibration energy, and it signed that the chemical
bond of Si-O-Al or Si-O-Si got stronger. The
increase of SiO2/Al2O3 mol ratios lead to the
decrease of vibration and intensity in wave number
of 3400 cm-1. It signed the loosing of water as a
result of polycondensation process in geopolymer.
In this cases, H-O-H bond getting weak.
506

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ISBN : 978 979 19201 0 0
SiO2/Al2O3=5.06
3448.72
972.12
%T
SiO2/Al2O3=5.0
3448.72
964.41
3448.72
956.69
SiO2/Al2O3=3.0
SiO2/Al2O3=2.0
964.41
3456.44
SiO2/Al2O3=0.5
3456.44
1010.70
4500
4000
3500
3000
2500
2000
1500
1000
500
-1
Wave Number (cm )
Figure 6 FTIR Spectra of Geopolymer with Variation of Al2O3 Moles
972.12
3448.72
SiO2/Al2O3=5.06
462.92
SiO2/Al2O3=5.0
%T
972.12
3448.72
455.20
SiO2/Al2O3=3.5
3433.29
972.12
447.49
SiO2/Al2O3=2.5
979.84 455.20
SiO2/Al2O3=1.5
3448.72
972.12 439.77
3448.72
4000
3000
2000
1000
-1
Wave Number (cm )
Figure 7 FTIR Spectra of Geopolymer with Variation of SiO2 moles

Microstructure Development by SEM
Geopolymer morphology in the micro scale has
been
investigated
by Scanning
Electron
Microscopy. SEM images of polished samples with
corresposnding SiO2/Al2O3 mol ratios are presented
in Figure 8, 9 and 10.
A significant change in
microstructure,
especially
homogeneity,
compactness, pores structure and some microcracks
were associated with changing SiO2/Al2O3 mol
ratios.
Proceeding Book
As shown in Fig.8, microstucture of SiO2/Al2O3 =

5.06 which was designed without any addition of
Al(OH)3. It shows a homogeneity and compactness
of geopolymer matrix, but some microcracks and
pores caused its final strength was lower than that
of SiO2/Al2O3 = 5.06 presented in Figure 8.(iii).
The latter figure shows more homogenous, more
compact, less porous and less fracture surfaces.
507

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ISBN : 978 979 19201 0 0
a
c
Figure 8 SEM Micrograph of Geopolymer with SiO2/Al2O3 = 5.06

a. geopolymer matrix, b. microcrack and fracture surface,
c. pores
SEM images of geopolymer with variation of
Al2O3 moles are presented in Fig. 9. Microstucture
of SiO2/Al2O3 = 0.5 shows grain structures, which
intergrains were not cemented. This exhibited less
compact structure and made it has the lowest final
strength. Microstucture of SiO2/Al2O3 = 2.0 was
more compact, with grain structure began to be
cemented, so it had final strength greater than
SiO2/Al2O3 = 0.5. Microstucture of SiO2/Al2O3 =
3.0 was the most wanted structure because its
matrix had homogenous and a good compactness,

although there were some residual (unreacted) fly
ash and some pores leading to the highest final
strength. Microstucture of SiO2/Al2O3 = 5.0
exhibited more unreacted fly ash and residual
matter, so its final strength decreased. Improvement
in microstructural homogheneity is conventionally
a strong indication of higher strength (De Silva,
2007).
(i) SiO2/Al2O3 =0.5
(ii) SiO2/Al2O3 = 2.0
e
d
(iii) SiO2/Al2O3 = 3.0
(iv) SiO2/Al2O3 = 5.0
Figure 9 SEM Micrograph of Geopolymer with Variation of Al2O3 Moles (a. grain structure,
b. Cemented grain structure, c. Dense matrix geopolymer, d. Pore, e. Unreacted fly ash)
Proceeding Book
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ISBN : 978 979 19201 0 0
SEM images of geopolymer with variation of SiO2

moles are presented in Fig. 10. Microstucture of
SiO2/Al2O3 = 1.5 showed needle structure with
some grains. This structure was caused by the ratio
of SiO2/Na2O which was very lower than the other
composition. There were no geopolymer matrix so
it exhibited the lowest strength. Microstucture of
SiO2/Al2O3 = 2.5 shows more cemented grain
structure with unreacted fly ash, so it caused more
strength than that of SiO2/Al2O3 = 1.5.

Microstucture of SiO2/Al2O3 = 3.5 showed
geopolymer matrix with some unreacted reactants
and pores so it reached high enough strength. While
microstucture of SiO2/Al2O3 = 5.0 showed dense
geopolymer matrix with some cracks and unreacted
fly ash. This matrix of SiO2/Al2O3 = 5.0 was so
compact that it had the highest strength in variation
of SiO2.
(i) SiO2/Al2O3 = 1.5
(ii) SiO2/Al2O3 = 2.5
f
d
e
(iii) SiO2/Al2O3 = 3.5
e
g
(iv) SiO2/Al2O3 = 5.0
Figure 10 SEM Micrograph of Geopolymer with Variation of SiO2 Moles

a. grain structure, b. needle structure, c. more cemented grain
structure, d. unreacted fly ash, e. geopolymer matrix,
f. Pores, g. cracks
Conclusions
Addition of aluminate species at constant silicate
and decrease of NaOH molarity made setting time
increase as there were more
Al(OH)3(H2O)
complex species prohibited polycondensation
reaction. The optimum compressive strength was
acieved at mol ratio of SiO2/Al2O3=3.0 for variation
of Al2O3 and SiO2/Al2O3=5.0 for variation of SiO2.
The total moles of the starting materials of both
variation were similar, but they were very different
in compressive strength because of the effect of
differences in SiO2/Na2O ratio. The phase
Proceeding Book
development shows that the greater SiO2/Al2O3 mol

ratio, the greater formation of amorphous
homogenous phase. It lead to reach optimum
SiO2/Al2O3 mol ratio. FTIR study shows that the
greater SiO2/Al2O3 mol ratio, the greater intensity
wave number of vibration meaning increasing of
the chain length Si-O-Al or Si-O-Si and increasing
vibration energy. It revealed that there were more
formation
of
gel
aluminosilicate
in
geopolimerisation and that the chemical bond of SiO-Al or Si-O-Si getting strong at optimum
SiO2/Al2O3 mol ratio. Grain structure appeared at
low SiO2/Al2O3 and it made lower strength, while
homogenous geopolymer matrix appeared at
509

January 24, 2009
ISBN : 978 979 19201 0 0
optimum SiO2/Al2O3 mol ratio and it lead to higher

strength. Unreacted fly ash and residual reactant
appeared at high SiO2/Al2O3 mol ratio caused a
lower strength geopolymer. In the SiO2-Al2O3Na2O-H2O
system,
all
component
are
interdependent relationship, so in this research there
was significant effect of Na2O and H2O, too.
References
Aly, Z., Vance, E. R., Perera, D. S., Hanna, J. V.,
Griffith, C. S., Davis, J., and Durce, D.,
(2008),
Aqueous
Leachability
of
Metakaolin-Based Geopolimers with Molar
Ratios of Si/Al = 1.5-4, Journal of Nuclear
Materials, Vol. 378, page 172-179.
Bakharev, T., (2005a), Gepolimeric Materials
Prepared Using Class F Fly Ash and
Elevated Temperature Curing, Cement and
Concrete Research, Vol. 35, page 12241232.
Bakharev, T., (2005b), Durability of Geopolymer
Materials in Sodium and Magnesium Sulfate
Solutions, Cement and Concrete Research,
Vol. 35, page 1233-1246.
Chindaprasirt, P., Chareerat, T., and Sirivivatnanon,
V., (2007), Workability and Strength of
Coarse High Calsium Fly Ash Geopolymer,
Cement and Concrete Composites, Vol. 29,
page 224-229.
Davidovits, J., (1991), Geopolymer : Inorganic
Polymeric New Materials, Journal of
Thermal Analysis, Vol. 3, page 1633-1656.
Davidovits, J., (1994a), Geopolimers : Man-Made
Rock Geosynthesis and the Resulting
Development of Very Early High Strength
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Vol. 16 (2&3), page 91-139.
Davidovits, J., (1994b), Properties of Geopolymer
Cements, Proceeding First International
Conference on Alkaline Cements and
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Binders and Materials, Kiev State Technical
University, Kiev, Ukraine, page 131-149.
Davidovits, J., (1994c), Recent Progress in
Concrete for Nuclear Waste and Uranium
Waste Containment, Journal of Concrete
International, Vol. 16, No. 12, page 53-58.
Davidovits, J., and Davidovics, M., (1991),
Geopolymer : Ultra-High Temperature
Tooling Material for the Manufacture of
Advanced
Composites,
Geopolymer
Tooling Material, Vol. 2, No. 36, page 19391949.
De Silva, P., Sagoe-Crenstil, K., and
Sirivivatnanon, V., (2007), Kinetics of
Geopolymerization : Role of Al2O3 and
Proceeding Book
SiO2, Cement and Concrete Research, Vol.

37, page 512-518.
Duxson, P., Mallicoat, S. W., Lukey, G. C., Kriven,
W., M., and van Deventer, J., S. J., (2007),
The Effect of Alkali and Si/Al Ratio on the
Development of Mechanical Properties of
Metakaolin-based Geopolimers, Colloids
and Surfaces A : Physicochemistry.
Engineering. Aspects, Vol. 292, page 8-20.
Duxson, P., Provis, J. l., Mallicoat, S. W., Lukey,
G. C., Kriven, W., M., and van Deventer, J.,
S. J., (2005), Understanding
the
Relationship
between
Geopolymer
Composition,
Microstructure
and
Mechanical Properties, Colloids and
Surfaces, Vol. 269, page 47-58.
Fansuri, H. (2008b), Personal Communication. 8th
October 2008.
Fernandez-Jimenez, A., Palomo, A., Sobrados, I.,
and Sanz, J., (2006), The Role Played by
Reactive Alumina Content in the Alkaline
Activation of Fly Ashes, Microporous and
Mesoporous Materials, Vol. 91, page111119.
Fletcher, R.A., MacKenzie, K. D. J., Nicholson, C.
L., and Shimada, S., (2005), The
Composition Range of Aluminosilicate
Geopolymers, Journal of The European
Ceramic Society, Vol. 25, page. . 1471-1477.
Hardjito, D., Wallah, S. E., Sumajouw, M. J.,
Rangan, B. V, (2004), Factors Infuencing
The Compressive Strength of Fly Ash-Based
Geopolymer Concrete, Dimensi Teknik
Sipil, Vol. 6, No. 2, page 88-93.
Kamhangrittirong, P. and Suwanvitaya, P., (2006),
The Effect of Fly Ash Content and Sodium
Hydroxide Molarity on Geopolymer,
International Conference on Pozzolan,
Concrete and Geopoymer, page 213-218.
Komnitsas, K. and Zaharaki, D., (2007),
Geopolimerisation : A Review and
Prospects for the Minerals Industry,
Minerals Engineering, Vol. 20, page 12611277.
Lee, W. K. W. and van Deventer, J. S. J., (2002),
The Effect of Ionic Contaminants on the
Early-Age of Alkali-Activated Fly Ash
Cement, Cement and Concrete Research,
Vol. 32, page 577-584.
Mishra, A., Choudhary, D., Jain, N., Kumar, M.,
Sharda, N., and Dutt, D., (2008). Effect of
Concentration of Alkaline Liquid and Curing
Time on Strength and Water Absorption of
Geopolymer Concrete. Asian Research
Publishing Network (ARPN) Journal of
Engineering and Applied Sciences, Vol. 3,
No. 1, page 14-18.
510

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ISBN : 978 979 19201 0 0
Palomo, A., Grutzeck, M. W., and Blanco, M. T.,

(1999), Alkali-Activated Fly Ashes, A
Cement for the Future, Cement and
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Phair, J. W., Smith, J. D., and van Deventer, J. S. J.,
(2003), Characteristics of Aluminosilcate
Hydrogels
Related
to
Commercial
Geopolymers, Materials Letters, Vol. 57,
page 4356-4367.
Rizain, (2008), Pelarutan Aluminium and Silikon
Berbagai Abu Layang Batubara dari Empat
PLTU Menggunakan Variasi Konsentrasi
NaOH and Temperatur, Tesis, Program
Magister FMIPA Institut Teknologi Sepuluh
Nopember, Surabaya.
Swaddle, T. W., (2001), Silicate Complexes of
Aluminum(III) in Aqueous Systems,
Coordination Chemistry Reviews, Vol. 219221, page 665-686.
Teixeira-Pinto, A. Fernandez, P., and Jalali, S.,
(2002), Geopolymer Manufacture and
Application Main Problems when Using
Concrete Technology, Proceeding of
International Conference on Geopolymer,
28-29 October, Melbourne, Australia.
van Deventer, J. S. J., Provis, L. J., and Lukey, G.
C., (2007), Reaction Mechanisms in the
Geopolymeric Conversion of Inorganic
Waste to Useful Products, Journal of
Hazardous Materials, Vol. A139, page 506513.
van Jaarsveld, J. G. S., and van Deventer, J. S. J.,
(1996), The Potential Use of Geopolymeric
Materials to Immobilize Toxic Metals : Part
I. Theory and Application, Journal of
Minerals Engineering, Vol. 10, No. 7, page
659-669.
van Jaarsveld, J. G. S., van Deventer, J. S. J., and
Lukey, G. C., (2003), The Characterization
of Source Materials in Fly Ash-Based
Geopolymers, Materials Letters. Vol. 57,
page 1272-1280.
van Jaarsveld, J.G.S. and van Deventer, J. S. J.,
(1996), The Potential Use of Geopolimeric
Materials to Immobilize Toxic Metals : Part
I. Theory and Applications, Minerals
Engineering, Vol. 10, No. 7, page 659-669.
Weng, L., Sagoe-Cretsil, K., Brown, T., and Song,
S., (2005), Effects of Aluminates on the
Formation of Geopolimers, Materials
Science and Engineering B, Vol. 117, page
163-168.
Xu, H. and van Deventer, J. S. J., (2000), The
Geopolymerisation of Alumino-silicate
Minerals, International Journal of Mineral
Processing, Vol. 59, page 247-266.
Proceeding Book
511

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Structural Shielding Design for Mobile X-Ray Units in Local Public Hospitals
in Yogyakarta.
Zaenal Abidin
Sekolah Tinggi Teknologi Nuklir-Badan Tenaga Nuklir Nasional
Jln Babarsari. P.O.BOX 6101 YKBB Yogyakarta 55281
Telp : (0274) 48085, 489716; Fax : (0274) 489715
E-mail : zaenala6@gmail.com
Abstract
A research has been conducted on the operation of mobile X-ray units in three local public hospitals in
Yogyakarta in order to determine the minimum thickness for safe structural shielding. Data were taken by
operating each machine 25 times, respectively, in 70 kV and 40 mAs. The level of radiation exposure was
then measured with the tube positions of vertical, axial, horizontal to determine the safe distance and shield
thickness. The result shows that the safe distance for the position beside the tube is 3.08 meters for the
operators and 12.02 meters for others, while for the position behind the tube, the safe position is 1.41
meters for both. The structural shielding needed is 1.5 mm lead (Pb) or 16 cm concrete.
Keywords: X-ray Mobile Unit, tube position, safe distance, structural shielding.
Introduction
Mobile X-ray systems are moved around hospitals
all the time to perform radiographic photography on
patients who cannot easily get into an X-ray room. In
operating the machine, we must be sure that it is safe
for the staffs, personnel or operators of the X-ray unit,
patients and other members of the public.
International regulations demand that diagnostic
and therapy departments are built to ensure that
radiology and radiotherapy staffs, personnel working in
the vicinity of a radiation source, patients and members
of the public are exposed to the minimum amount of
radiation[1].
Local public hospitals in Yogyakarta which possess
the facility of x-ray mobile units rarely use them in the
treatment room (in situ) due to the fact that the safe
distance from the radiation shining is not yet known
concerning the radiation exposure[2]. This research will
reveal how much the radiation exposure is, what the
safe distance is and how to design the required
structural shielding.
Theory
The basic principles of external radiation
protection are lengthening the distance, shortening the
shining exposure, and using appropriate radiation
shield. A mobile X-ray machine is a source of external
radiation. Therefore, for protection from external
Proceeding Book
radiation, make sure to use shortest time with

the radiation, and farthest possible distance for
radiation, and the necessary thickness of
radiation shield.
The formula in calculating radiation and
distance is a reversed square:[3]
Dr = K
1
r2
or Dr . r2 = K
so
Dr1 . r12 = Dr2 . r22 = Dr3 . r32 = K
[1]
where:
K is a constant which depends on the source,
Dr1 is dose rate at distance r1,
Dr2 is dose rate at distance r2, and
Dr3 is dose rate at distance r3.
The purpose of radiation shielding is to
limit radiation exposures to human beings (both
workers and the public) to an acceptable level.
Shielding of X-ray machines consists of two
kinds: tube housing shielding and structural
shielding.
X-ray tube housing shielding of energies less
than 500 KV, in accordance with NCRP
(National Council on Radiological Protection
and Measurement) shall have the maximum
leakage dose of 1 R/hr[1].
Primary protective barrier is the wall of
x-ray room designated to face primary rays or
512

January 24, 2009
ISBN : 978 979 19201 0 0
useful beam and the secondary protective barrier is

intended to shield Leakage radiation from the tube
housing and scattered radiation from the machine.
Primary Protective barrier (Barrier against Useful

Beam)
dpri
The attenuation or the number of Roentgens per milli

Ampere minutes in a week for the useful beam
normalized at one meter, K[4] (see Fig.1)
P.(d pri ) 2
[2]
K=
R / mA - min at 1 m
WUT
W
U
T
= permissible dose 0.1 R/week for

Radiation Worker (Controlled Area) or
0.01 R/week for Non Radiation Worker
(Non Controlled Area)
= distance between focus and point of
interest
= work load (mA-minutes)/week
= Use factor (U=1 for Floor, and U
=0.25 for walls)
= Occupancy factor
By calculating the K value, we can determine

the thickness of Primary Protective barrier by
plotting K value to the graph for certain kV of
Fig.1
Figure 1 Attenuation in lead of x-rays produced by potentials of 50 to 200 kV.[4]

Secondary Protective Barrier (Barrier against Leaked
Radiation)
The transmission factor B[4] is
P.(dsec ) 2 .60.I
B=
W .T
Where:
Proceeding Book
[3]
dsec
W
T
= permissible dose 0.1 R/week for

Radiation Worker (Controlled Area) or
0.01 R/week for non Radiation Worker
(Non Controlled Area)
= distance between focus and point of
interest
= work load (mA-minutes)/week
= Occupancy factor
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January 24, 2009
ISBN : 978 979 19201 0 0
= milli Ampere
Device and material
To determine the thickness of secondary protective

barrier against leakage radiation transmission factor B
is equal to
B = (1 / 2) n
n = X / HVL
[4]
Where:
X
= thickness of Secondary protective barrier
against leakage radiation
HVL
= Half Value Layer
Secondary Protective Barrier (Barrier against
Scattered Radiation)
The attenuation or the number of Roentgens per milliAmpere minutes in a week for the useful beam
normalized at one meter, K (see Fig.1). We take Fig.1
because of by assuming that the energy of the scattered
radiation when the X-rays are generated at 500kV or
less, is equal to the energy of the useful beam [4]
K=
P
dsec
dsca
W
T
F
P.(d sec ) 2 .(d sca ) 2 .400

a.W .T .F
[5]
=permissible dose 0.1 R/week for Radiation

Worker (Controlled Area) or 0.01 R/week for
Non Radiation Worker (Non Controlled Area)
=distance between focus and point of interest
= distance between focus and scattered
=work load (mA-minutes)/week
=Occupancy factor
=Area of scattered to incident exposure at 1
meter from the scattered
By calculating K value, we can determine the

thickness of the Secondary Protective barrier against
scattered radiation by plotting K value to the graph for
certain KV of Fig. 1 above.
If the thickness of required barrier for leakage
and scattered radiations is found to be approximately
the same, one HVL should be added to the larger one
to obtain the required total secondary barrier thickness.
If the two differ by at least one TVL, the thicker of the
two will be adequate.
Selecting the material and form used for the
structural radiation shield is based on the number of
radiation energy exposed to be attenuated, the barrier
function, factors of practicality and efficiency in usage,
storage, and economical, as well as the rules by
Department of Health in 1999[6]. The selected material
is lead (Pb) plat of 2 mm thick with the U-form [7].

Proceeding Book
Survey meter was used in measuring the

radiation secondary exposure, roll meter in
measuring distance, and warning sign lamps,
film badge (to record the individual radiation
dose), mobile X-ray machines (Siemens DSA-7),
and protective lead apron.
Activity
Data were taken by operating each machine 25
times in three hospitals: Regional Public
Hospital (RPH) Yogyakarta, RPH Sleman, and
RPH Wonosari Gunung Kidul, by measuring
the dose rate at the distances of 2.24 m and 1.41
m from tube placed as high as the gonad, using
the protection procedure taken with exposure at
70kV/40mAs. The data were recorded and
calculated using the formulation explained
above. Shining was conducted to the object of a
fat body by 70kV and 40mAs. Focus film
distance (FFD) is 1 meter and then pulled aside
2 meters with the farthest assumption distance
of patients bed, so the distance r1 is 2.24 meters
from the focusing tube, while for the behind
position used FDD one meter, and distance of r1
is 1.41 meter from the focusing tube; such a
distance is assumed as the distance of the
worker in standing position.
The Calculation
Calculation taken into consideration by using
the formulations above concerning with the
condition of:
Orientation factor (U)[5]
If the radiation beam is oriented in
some particular direction for more than
50 per cent of the time when the device
is in use, then a value of U = 1 is used
for specifying the shielding in this
direction.
If the radiation beam is oriented in
some particular direction for less than
50 per cent of the time when the device
is in use, then a value of 0.25 < U < 1
may be used for specifying the
shielding. However, the orientation
factor must always be no smaller than
the proportion of time in use for which
the beam is oriented in this direction.
514

January 24, 2009
ISBN : 978 979 19201 0 0
A value of U = 1 is used in directions affected

only by leakage and scattered radiations.
Occupancy factor (T)
A value of T = 1 is used in working premises
and, in the case of medical use of radiation,
also in waiting rooms and patient rooms.
A value of 0.1 < T < 1 may be used in indoor
or outdoor premises where human beings do
not remain on a continual basis (e.g. WCs,
corridors, storerooms or streets). However, the
occupancy factor shall always be no smaller
than the proportion of time during which
human beings occupy the area concerned.
Result and Discussions

In the medical radiography, the technique of
taking pictures, i.e. the tube position, is determined by
patient condition. The position and function of the tube
should be as follows:
Table 1. Tube Position and Function [2]
No
1.
Position
Vertical
2.
Axial
35o
3.
Horizont
al
Function
Taking
pictures
of
cranium, cervical, thorax,
abdomen, pelvis, thoracic
vertebrae, lumbosacral
vertebrae, for high and
low extremities.
Taking pictures of thorax
with
the
patients
position half seated,
abdomen
with
the
patients position half
seated, and cranium with
townes position
Taking
pictures
of
cranium lateral, cervical
lateral, and abdomen
with
the
patients
position of LLD (Lateral
Left Dicubitus)
For RPH Yogyakarta, the pause time is assumed

10 minutes, shining is conducted for 144 times each
day, 7 days a week, at each exposure uses the current
rate of 40 mAs,70 kV. So the total number of exposure
is 1008 times per week.
Workload W
= 1008 exposure/week X 40mAs:
60(min/s)
= 672 mA.min/week
Proceeding Book
Calculating the thickness of Shielding for

Primary Radiation
P (maximum exposure allowed) is 0.1 (for
controlled area), and 0.01 (for uncontrolled
area), the distance (d) = 2 m, W= 672
mA.min/week, U (Use Factor) = for wall and
1 for floor.
T (Occupancy Factor)
:1
(active room)
a.Wall A = primary radiation = horizontal beam
Kwall A
= 0.002 R/mA-min = 2 x 10-3
R/mA-min.
Based on reference 6, to obtain the required
attenuation for the curve 125 kVp we need the
lead (Pb) thickness of 1.5 mm while to get the
same attenuation for concrete the thickness
needed is 12.7 cm.
b.Floor = primary radiation = Vertical Beam
Kfloor = 0.000067 R/mA-men = 7 x 10-3 R/mAmin.
Based on reference 8, the thickness required is
2.8 mm for lead or 21.895 cm for concrete.
Calculating the thickness of Shielding for
Secondary Radiation
Wall B
a.
Wall B = scattered radiation = Vertical
beam
Given:
P
= 0.01 R (uncontrolled area)
W
= 672 mA-min/week
=1m
dSCA
T
=1
= 1.4 m
dSEC
F
= 38.3087 cm2
a
= 0.0015 (90O)
f
=1
KUX
= 0.2072
Based on reference 6, the thickness required for
radiation shielding is 0.2 mm for lead or 0.5 cm
for concrete.
b.Wall B = scattered radiation = Horizontal
beam
Given:
P
W
= 672 mA-min/week
= 1.5 m
dSCA
T
=1
= 1.803 m
dSEC
F
= 86.1948 cm2
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a
f
KUX
= 0.0015 (45O)
=1
= 0,3367
From the curve for 125 kVp the required thickness for
radiation shielding is 0.13 mm for lead or 0 cm for
concrete.
c.Wall B = scattered radiation = Horizontal beam
Given:
P
W
= 672 mA-min/week
= 1.5 m
dSCA
T
=1
= 1.803 m
dSEC
F
= 86.1948 cm2
a
= 0.0015(90O)
f
=1
KUX
= 0,3367
e. Wall B = leaked radiation = Vertical beam

Given:
P
W
= 672 mA-min/week
d
= 1.414 m
T
=1
I
= 125 mA
BLx
= 2.2315
= n
BLx
2.2315 = n
n
= -0.2895
Because the result of n is negative, then the
leaked radiation is not taken into account, so
that there is not shielding required for leaked
radiation.
radiation shielding is 0.13 mm for lead or 0 cm for
concrete.
d. Wall B = scattered radiation = Horizontal beam
Given:
P
W
= 672 mA-min/week
= 1.5 m
dSCA
T
=1
dSEC
= 1.803 m
F
= 86.1948 cm2
a
= 0.0025 (135O)
f
=1
= 0.2020
KUX
radiation shielding is 0.2 mm for lead or 0.5 cm for
concrete.
f. Wall B = leaked radiation = Horizontal beam

Given :
P
= 0.01 R
W
= 672 mA-min/week
d
= 1.803 m
T
=1
I
= 125 mA
= 3.628
BLx
= n
BLx
3.628 = n
n
= -0.4648
Again, because the result of n is negative, then
the leaked radiation is not taken into account, so
that there is not shielding required for leaked
radiation.
The safe distances for radiation exposure from
the mobile X-ray machines in the three hospitals
can be seen in the tables below.
Table 2. Result of measurement mobile x-ray machine in RPH Senopati Bantul

No
Tube
position
Patients
bed
position
Distance
patients
bed
r1(m)
Average
Dose
scatter
(mrem)
D1
(mre
m/s)
Vertical
Beside
tube
2.24
0.018
0.009
Axial
350
Beside
tube
2.24
0.01
0.005
Proceeding Book
DVL (D2)
Mrem/s
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
r2 =
D1 xr12
D2
Safe
distance (m)
8.06
14.73
25.51
6.01
10.98
19.01
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Axial
350
Behind
tube
1.41
0.00
0.000
horizon
tal
Beside
tube
2.24
0.01
0.005
horizon
tal
Behind
tube
1.41
0.00
0.000
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
Safe
6.01
10.98
19.01
Safe
Table 3. Result of measurement mobile x-ray machine in RPH Sleman

No
Tube
position
Patients
bed
position
Distance
patients
bed
r1(m)
Average
Dose
scatter
(mrem)
D1
(mre
m/s)
Vertical
Beside
tube
2.24
0.018
0.009
Axial
350
Beside
tube
2.24
0.014
0.007
Axial
350
Behind
tube
1.41
0.00
0.000
horizon
tal
Beside
tube
2.24
0.04
0.002
horizon
tal
Behind
tube
1.41
0.00
0.000
DVL (D2)
Mrem/s
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
r2 =
D1 xr12
D2
Safe
distance (m)
8.07
14.73
25.51
7.11
12.99
22.50
Safe
3.80
6.94
12.02
Safe
Table 4. Result of measurement mobile x-ray machine in RPH Wonosari Gunung Kidul
No
Tube
position
Patients
bed
position
Distance
patients
bed
r1(m)
Average
Dose
scatter
(mrem)
D1
(mre
m/s)
Vertical
Beside
tube
2.24
0.01
0.005
Axial
350
Beside
tube
2.24
0.01
0.005
Axial
350
Behind
tube
1.41
0.00
0.000
horizon
tal
Beside
tube
2.24
0.002
0.005
Proceeding Book
DVL (D2)
Mrem/s
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
694E-6(worker)
208E-6(staff)
694E-6(public)
r2 =
D1 xr12
D2
Safe
distance (m)
6.01
10.98
19.01
6.01
10.98
19.01
Safe
3.80
6.94
12.02
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horizon
tal
Behind
tube
1.41
0.00
0.000
694E-6(worker)
208E-6(staff)
694E-6(public)
Safe
Using the formulations above, the shielding can presented in the table below.
Table 5. Result of thick shielding calculation for structural shielding
Location
K (R/
mA - minut
week
6 . 10-5
2 . 10-3
2.07 . 10-1
3.37 . 10-1
3.37 . 10-1
2.02 . 10-1
1.295 . 10-1
5.18 . 10-1
5.18 . 10-1
3.11 . 10-1
3.367 . 10-1
4.656 . 10-1
4.656 . 10-1
2.793 . 10-1
3.7291
7.3090
Floor / Primer
Wall A / Primer
Wall B/ scattering
Wall B/ scattering
Wall C/ scattering
Wall C/ scattering
Wall D/ scattering
Wall D/ scattering
Ceiling /scattering
Ceiling /scattering
Thickness(mm)
Lead
Direction
Vertical
Horizontal
Vertical
2.,8
1.5
0.2
0.13
0.13
0.2
0.33
0.06
0.06
0.13
0.13
0.1
0.1
0.13
0
0
Horizontal
Vertical
Horizontal
Vertical
Horizontal
Vertical
Horizontal
Thickness
(cm)
concrete
21.895
12.7
0.5
0
0
0.5
0
0
0
0
0
0
0
0
Table 6. The calculation of Leak radiation

Location
Direction
BLx = n
= P x (d) x 600 x I
Wx T
Wall B
Wall C
Wall D
Ceiling
Vertical
Horizontal
Vertical
Horizontal
Vertical
2.2315
3.6280
1.3950
5.5800
3.2810
-0.2895
-0.4648
-0.1201
-0.6201
-0.4649
Horizontal
Vertical
Horizontal
5.0161
151.7882
111.6071
-0.5817
-1.8117
-1.7007
Discussion
NCRP (National Council on Radiological
Protection and Measurement) recommends that the
maximum permissible dose is 25 Sv/hr (2.5 mrem/hr)
for radiation workers, 7.5 Sv/hr for staff, and 2,5
S3v/hr.(0.25 mrem/hr) for public[6]. In this research,
Proceeding Book
using the closest distance assumption among the

patients beds 1,5 meters and FFD 1 meter, it
was found that the distance of r2 was 1.80
meters from the tube. After that, the results of
calculating the dosage rate (D2) in each hospital
can be seen in Table 7, 8 and 9.
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Table 7. Dose rate in RPH Senopati Bantul
No
1.
2.
3.
4.
5.
Tube position
D1
(mrem/s)
r1
(m)
0.009
0.005
0.000
0.005
0.000
2.24
2.24
1.41
2.24
1.41
Vertical
Axial 350
Axial 350
Horizontal
Horizontal
r2
(m)
Patients bed
Beside tube
Beside tube
Behind tube
Beside tube
Behind tube
1.80
1.80
1.80
1.80
1.80
D2
(mrem/s)
0.0139
0.0077
0.0000
0.0077
0.0000
Table 8. Dose rate in RPH Sleman
No
1.
2.
3.
4.
5.
Tube position
Vertical
Axial 350
Axial 350
Horizontal
Horizontal
D1
(mrem/s)
r1
(m)
0.009
0.007
0.000
0.002
0.000
2.24
2.24
1.41
2.24
1.41
Patients bed
Beside tube
Beside tube
Behind tube
Beside tube
Behind tube
D2
(mrem/s)
r2
(m)
1.80
1.80
1.80
1.80
1.80
0.0139
0.0108
0.0000
0.0031
0.0000
Table 9. Dose rate in RPH Wonosari Gunung Kidul
No
1.
2.
3.
4.
5.
Tube position
Vertical
Axial 350
Axial 350
Horizontal
Horizontal
D1
(mrem/s)
r1
(m)
0.005
0.005
0.000
0.002
0.000
2.24
2.24
1.41
2.24
1.41
Patients bed
Beside tube
Beside tube
Behind tube
Beside tube
Behind tube
Based on the tables above, calculating the

design of safe structural barrier in the U-form (see in
Fig 3 & Table 5), the highest load is for RPH Sleman,
which is then taken as the standard for the other two
hospitals for more safety. The calculation result
requires the structural barrier with the thickness of 1.5
mm (rounded to 2 mm) for lead wall or 16 cm for
concrete wall, and 2.8 mm for lead floor [6].
2.
(1)
The assumption that the closest distance among

the patient beds is 1.5 meters beside the tube
proved to be unsafe for the workers. The closest
safe distance beside the tube is 3.80 meters for the
workers and is 12.02 meters for public. While for
the position behind the tube, the closest safe
distance for both the workers and public is 1.41
meters.
Proceeding Book
1.80
1.80
1.80
1.80
1.80
D2
(mrem/s)
0.0077
0.0077
0.0000
0.0031
0.0000
Based on the calculation, the minimum

thickness required for safety shield for the
primer radiation is 1.5 mm for lead (Pb)
wall or 16 cm for concrete wall, and 2.8
mm for lead floor.
References
Conclusion
1.
r2
(m)
(2)
(3)
NCRP, 2004, Structural Shielding

Design for Medical X-ray Imaging
Facilities, Report No. 147 (Revised
March 2005), NCRP Bethesda, MD.
Abidin Z.,Toto K.& Taufiq Z.,2008, The
Operation of X-ray Mobile Unit in Three
Local Public Hospital in Yogyakarta,
Proceeding Seminar NHI &GTN, ISSN
No 1693-3346 page 119-125, Jakarta.
Taufiq Z, 2008, The Analysis of Safety in
The Operation of X-Ray Mobile Unit in
The Care Room of The Regional State
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ISBN : 978 979 19201 0 0
(4)
(5)
Hospital in Yogyakarta, Final Report in POIN,

Yogyakarta.
Cember H, Introduction to Health Physics,
Second Edition, Pergamon Press, 1985. .
Simpkin DJ, Dixon RL. Secondary Shielding
Barriers for Diagnostic X-Ray Facilities:
Scatter and Leakage Revisited. Health Phys
1998;74:35065.
(6)
(7)
NCRP, 1976, Structural Shielding

Design and Evaluation, Report No. 49
(September 1976), NCRP
Bumiasih T, 2008, The Design of The
Radiation Shielding of The X-Ray
Generator in Distric General Hospital
Yogyakarta City, Final Report in POIN,
Yogyakarta.
Figure 2 Scheme of the existing shielding in most hospital
Proceeding Book
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Wall D
Wall B
Wall C
Peeping window
Wall D. Side orientation
Supporting frame made from steel plat of 3 mm thick and

3,2 cm wide
Figure 3 Design of Structural Shielding
Proceeding Book
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MgF2 as Catalyst and Support on Phenol Acylation

Nisa Nurina Valerie and Irmina Kris Murwani *
Chemistry Study Program, Faculty of Mathematics and Natural Sciences,
Sepuluh Nopember Institute of Technology,
Keputih ITS Campuss, Sukolilo, Surabaya, Indonesia, 60111.
*e-mail : irmina@chem.its.ac.id
Abstract
The using of MgF2 as catalyst and support for phenol acylation with acetic acid has been studied. The
reaction is an alternative method to reduce the phenol concentration. Generally, the acylation reactions
involve the use of Lewis acid catalysts. MgF2 is one of the non toxic Lewis acid catalysts. MgF2 in this
research were prepared and characterized using X-ray diffraction (XRD), Fourier Transform infrared
spectroscopy (FTIR) and measurement of specific surface area with N2 adsorption. The catalytic activities
were determined based on phenol conversion. Result of this research indicated that MgF2 and CuO/MgF2
serve the purpose of supported catalyst with phenol conversion 95.23 and 90.53%, respectively. This
conversion value showed a linear correlation with its specific surface area, that is 31.38 and 12.75 m2/g,
respectively. Analysis of phenol acylation using HPLC showed that acetophenone was the main product
with selectivity MgF2 45.37% and CuO/MgF2 52.32%.
Keywords: Catalyst, MgF2, phenol acylation, support.
Introduction
Phenol acylation is an important and frequently used
organic transformation as it provides not only an
efficient and inexpensive route for the protecting
hydroxy group but also produced important organic
intermediates in multi-step synthetic processes which
are widely used in the synthesis of fine chemicals,
pharmaceuticals, perfumes, plasticizers, cosmetics,
chemical auxiliaries, etc. [6]. Hidroxyacetophenones
(HAP) which are useful intermediates for the
manufacture of pharmaceuticals can be obtained
through catalytic rearrangement of phenyl acetate or
direct acylation of phenol by acetic acid [9]. In
particular, p-HAP is widely used for the synthesis of
paracetamol and o-HAP is a key intermediate for
producing 4-hydroxycoumarin and warfarin, which
are both, used as anticoagulant drugs [8]. Acylation is
normally achieved by treatment with acetic acid in the
presence of suitable catalysts. Homogeneous catalysts
such as AlCl3, CoCl2, CuCl2, FeCl3 and TiCl5 have
been used for the acylation of phenol. However, one
of the major problems in homogeneous reaction is the
separation of the catalyst from the reaction mixture.
Heterogeneous catalysts are found to be very good
alternatives to the problems associated with proton
acids (Lewis acids) or Friedel-Crafts type catalysts
[2,8,12]. Phenol acylation with acetic acid over MgF2
and copper oxide catalyst supported on MgF2 was
Proceeding Book
investigated. The aim of this investigation is also to

study the effect of copper oxides on MgF2 during
acylation. The catalysts were characterized by various
techniques like XRD, FTIR and BET surface area.
MgF2 as Lewis acid is one candidate as support and
catalyst.

Catalyst preparation and characterization
Magnesium fluoride was prepared according to the
literature [14]. The copper oxides catalyst supported
on MgF2 was prepared by wet impregnation method.
The support was impregnated with Cu(ClO4)2 in
water followed by drying. This precursor was
activated by calcinations at 400C for 4 h. Catalysts
characterization was carried out by means of XRD,
FTIR and BET. XRD characterization was performed
using XRD JEOL JDX-3530 (Cu K). FTIR
characterization was performed using Shimadzu
FTIR-8400S with DRS-8000. Specific surface areas
were determined by means of N2 adsorption measured
with Quantachrome NovaWin2-Data Acquisition and
Red for NOVA instruments version 2.1.
Catalytic activity on phenol acylation
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The catalytic properties of the catalysts were

determined using HPLC method. Phenol acylation
were carried out in magnetically stirred glass reactor
at the following reaction conditions: reaction mixture
= catalyst + acetic acid + phenol, temperature = 25C,
reaction period = 15 minutes. The catalytic activity
was observed based on concentration of phenol
conversion. The catalytic selectivity was observed
based on acetophenone product formed.

MgF2 Catalyst
Fig. 2. FTIR spectra of MgF2
This paper reports results on obtaining magnesium
fluoride in the sol-gel reaction of magnesium nitrate
hexahydrate and hydrofluoric acid, according to the
equation below:
Mg(NO3)2.6H2O + 2HF MgF2 + 2HNO3 +
6H2O
Powder X-ray diffractogram of MgF2 is shown
in Fig. 1. The sharp diffraction lines at d = 3.275 ,
2.231 and 1.711 (2 values are 27.2, 40.4 and
53.5, respectively) are due to the tetragonal form of
magnesium fluoride (PDF No. 06-0290). No
diffraction
lines
noticed
corresponding
to
Mg(NO3)26H2O, MgO or other contaminants
detected.
CuO/MgF2 catalyst
The impregnated sample was dark gray in color,
which suggests that copper oxide phase exists in the
sample. The copper oxide phase was formed during
calcinations [13]. The X-ray diffraction patterns of
CuO/MgF2 and MgF2 are presented in Fig. 3 below.
The XRD profile of CuO/MgF2 sample exhibits the
characteristic features of copper oxide as monoclinic
phase (PDF No. 72-0629) with the characteristic
peaks at at d = 2.5226 , 2.3217 and 1.7113 (2
values are 35.6, 38.7 and 53.5, respectively) and
the characteristic features of magnesium fluoride as
tetragonal phase (PDF No. 06-0290) with the
characteristic peaks at 2 = 27.2, 40.4 and 53.5.
Fig. 1. X-ray diffractogram of MgF2

FTIR spectra of magnesium fluoride is shown in
Fig. 2. A stretching vibration for the OH bond
appears at 3600-3200 cm-1. A bending vibration of
the HOH bond appears at 1648.2 cm-1 [5]. During
the preparation of magnesium fluoride, or when it is
contacted with water vapour, water dipoles interact
with coordinatively unsaturated Mg ions and fill their
coordination sphere. This leads to the formation of
surface hydroxyls. The stretching vibration for the
MgF bond appears at 1200 cm-1, 1000 cm-1, 730 cm1
and 458 cm-1 [3,11,14].
Proceeding Book
Fig. 3. X-ray diffractograms of CuO/MgF2 and

MgF2 (, : CuO)
The copper oxide phase giving strong reflections
only at 2 = 38.7 appeared in the sample prepared
by impregnation with copper loading of 2.35 wt. %.
Diffraction pattern of CuO/MgF2 show a strong
characteristic features of MgF2. This indicated that
the CuO species particles, which are amorphous or
very small, are highly dispersed within the matrix [5].
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The FTIR spectra of CuO/MgF2 reported in Fig.

4. The spectra have a broad absorption band at
approximately 3550-3200 cm-1, which is assigned to
the OH stretching vibration of waters. Similarly, the
band near 1630-1600 cm-1 is associated with the
bending mode of OH groups of adsorbed water [5].
The stretching vibration for CuO bond appears at
1500 cm-1 and 500 cm-1 [4,13] and the stretching
vibration of MgF appears at 1000 cm-1, 730 cm-1 and
458 cm-1 [3,11,14].
[6]. Phenol acylation done at optimum condition

obtained maximum catalyst activity. Activity is
ability of catalyst in conversion reactant to become
product wanted. Catalyst activity was determined
based on concentration of phenol conversion that
measured based on concentration of remains phenol.
Phenol detected on HPLC is phenol that was not
reacted or remains phenol. Smaller concentration of
remaining phenol, hence ever greater converted
phenol yielded. Optimum conditions at phenol
acylation as according to report from [6], at
temperature 25C for 15 minutes. Fig. 6 presents the
activity and selectivity of MgF2 and CuO/MgF2
catalysts.
Fig. 4. FTIR spectra of CuO/MgF2

Surface area measurement
The specific surface areas of the catalysts is given in
Table 1. The data indicate that the impregnation of
magnesium fluoride with an aqueous solution of
copper perchlorate reduces the surface area and the
pore volume of the samples, while increasing the pore
size. This is probably due to a certain contribution of
the CuO to the total surface area: a microporous
system is not well developed in CuO (surface area
1,10 m2/g) [5]. CuO/MgF2 showed a clear decrease in
surface areas and average pore diameters relative to
their supports. This is expected because the pores in
each support are partially filled by copper oxide
particles.
Table 1. BET characterization of MgF2 and
CuO/MgF2
Catalyst
Surface Area (m2/g)
MgF2
31,38
CuO/ MgF2
12,75
Catalytic activity on phenol acylation
The catalytic activity of samples was examined in
phenol acylation with acetic acid using HPLC
method. Acetic acid can be employed as acylating
agent because stable and its handling are easier than
acetic anhydrides [9]. Phenol acylation under solvent
free condition and the using of acetic acid as
acylating agent, hence reaction can take place faster
Proceeding Book
Fig. 6. The activity and selectivity of MgF2 and

CuO/MgF2 at room temperature
Higher conversion was obtained for catalyst MgF2
reach 95.23%. The activity of copper oxide catalyst
supported on MgF2 was lower with phenol
conversion reach 90.53%. Introduction of copper
oxide caused a decrease in catalytic activity. The
degree of conversion depends on the surface area of
catalysts, where MgF2 shows surface area was higher
than CuO/MgF2. Phenol conversion also can yield
acetophenone product [1]. The copper oxide catalyst
supported on MgF2 have proved more selective in
phenol acylation than those MgF2 itself. Highest
product of acetophenone was obtained by CuO/MgF2
and declines when applied by MgF2. From the above
characterization of catalysts, we conclude that the
differences of selectivity would not be related to the
specific surface area data. The state and distribution
of Cu species in the catalysts are the key factors to
the reaction. Based on the above results, we can
conclude that the catalytic activity was related to the
surface area of catalysts. All catalysts showed good
catalytic activity for phenol acylation, which can be
ascribed to the highest activity of each catalyst.
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Conclusion
MgF2 proved to be an interesting catalyst and
support for copper oxide catalyst in phenol acylation.
This result can be ascribed to the highest activity of
each catalyst. The experiment results showed that
percentage of phenol conversions using the MgF2 and
CuO/MgF2 catalysts were 95.23 and 90.53%,
respectively. This conversion showed a linear
correlation with surface area of each catalyst, that is
31.38 and 12.75 m2/g, for MgF2 and CuO/MgF2,
respectively. Analysis of the acylation product
showed that the acetophenone was the main product
of the acylation with selectivity MgF2 45.37% and
CuO/MgF2 52.32%.
[8]
Acknowledgements
[12]
[9]
[10]
[11]
We gratefully the support from LPPM ITS for

financial support
[13]
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
Baltrok, I.M., Aliyan, H., Khosropuur, A.R.

2001. Bismuth(III) salts as convenient and
efficient catalysts for the selective acetylation
and benzylation of alcohols and phenol.
Tetrahedron Lett. 57: 5851-5854.
Chandrasekhar, S., Ramachander, T., Takhi,
M. 1998. Acylation of alcohols with acetic
anhydride catalyzed by TaCl5: Some
implications in kinetic resolution. Tetrahedron
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Kim, Y.G., Chung, J.S., Nam, I.S. 1998.
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MgF2. J. Phys. Chem. A. 102: 7913-7918.
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over Cu- and Ag-NaY catalysts with aqueous
hydrogen peroxide. Mater. Research Bull. 42:
2170-2183.
Haber, J., Wojciechowska, M., Zielinski, M.,
Przystajko, W. 2007. Effect of MgF2 and
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under solvent free conditions. J. Mol. Catal. A:
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Kumar, P., Mirajkar, S.P., Kumar, R. 2004.
Cerium-containing MCM-41 materials as
Proceeding Book
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Gen. 298: 225-231.
525

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The Relation between The First Step Hydrothermal Temperature and Zeolites
Distribution on Synthesis of Zeolite from Fly Ash
Aulia Rochmah, Hamzah Fansuri
Institut Teknologi Sepuluh November (ITS) Surabaya
Keputih Sukolilo Surabaya, East Java, Indonesia
Corresponding Author: h.fansuri@chem.its.ac.id
Abstract
This research investigates the relation between the first step hydrothermal temperature on the
synthesis of zeolite from fly ash and the zeolite distribution. The zeolite quantities were
calculated by Quantitative X-Ray Powder Diffractions (QXRPD) using Rietveld refinement
method supported by XRF and Cation Exchange Capacity (CEC) data. Different compositions
of three mixed zeolite phases, i.e K-Chabazite, K-Phillipsite, and K-F, were formed at different
first step hydrothermal temperature, i.e 100, 120, 150 and 180 oC, and second hydrothermal
reaction at 100 oC for 6 to 96 hrs on synthesis of zeolite from fly ash. The differences between
calculated weight percentage of oxide of zeolites XRF data was due to the existences of oxides
in unidentified phases and amorphous phases. The differences between calculated CEC and
experiment were caused by exchangeable cations of other phases. It was found that zeolite
crystallization time was shorter when the first step hydrothermal temperature was higher.
Keywords: Zeolite synthesis, Zeolite from fly ash, Quantitative XRD
Introduction
Fly ash is one of the solid wastes generated in coal fired
power stations which has harmful effect on
environment. One of the environmental friendly efforts
of fly ash utilizations is fly ash conversion into zeolite
materials. Many methods of zeolite synthesis from fly
ash hydrothermally has been explored, i. e direct
conversion [14, 15, 16], fusion methods [2, 4, 17], and
extraction methods [6, 8]. Direct zeolite synthesis
procedures have shorter stages then indirect conversion
such as fusion and extraction methods. Although the
direct conversion produce lower purity then those two
methods, the zeolite products have reasonably high
cation exchange capacity (CEC) (175 meq/100 g
zeolites [14]). Thus, for lower grade zeolite such as
fertilizers, the zeolite synthesis from fly ash by direct
conversion is still feasible.
Zeolite synthesis from fly ash by direct
conversion has been conducted before by Muasyaroh et
al. [13] hydrothermally using potassium hydroxide as
alkali sources. More than one type zeolites was
obtained, i.e K-Chabazite, K-Phillipsite, and K-F [13].
However, the zeolite quantities have not been
determined, then it is not known the relation between
the reaction conditions and zeolite formed distributions.
It was reported that step-change of synthesis
Proceeding Book
temperature during hydrothermal treatment reduce by

half of the total synthesis time [9]. Moreover,
Muasyaroh et al. [13] also showed that higher first step
hydrothermal temperature could improve dissolution of
silica and alumina in fly ash and shorten the zeolite
crystallization time.
The aims of the present work were to explore
the relation between the first step hydrothermal
temperature and zeolite formed distributions, in order to
provide another method for synthesis certain zeolite
type from fly ash with specific properties.

Experimental
Zeolite materials was obtained from Muasyaroh, et al.
[13] that were synthesized from fly ash using variation
of first step hydrothermal temperature at 100, 120, 150,
and 1800C for 3,5 hours then continued by second
hydrothermal temperature at 100oC for 6, 24, 48, and 96
hours.
The zeolites were characterized by XRD, XRF
and CEC determinations. XRD analysis was carried out
by adding 20% internal standard of Rutile to samples
that contain zeolite phases. The diffractograms obtained
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ISBN : 978 979 19201 0 0
was analyzed quantitatively by Rietveld refinements

method using RIETICA software. The chemical
composition was measured using XRF and the CEC was
determined by ammonium acetate methods.
Diffractogram of samples were analyzed qualitatively

using XPert Grafic and Identify Software. Table 1
shows the identified phases found as a result of
variations on the first step hydrothermal temperature i.e
Mullite (PDF 15-0776), Quartz (PDF 05-0490),
Hercynite (PDF 34-0192), Magnetite (PDF 02-1035),
Kaliophilite (PDF 11-0313), K-Chabazite (PDF 440250), K-Phillipsite (PDF 16-0715), K-F (PDF 250619), Kalsilite (PDF 33-0988).
Table 1. Identified Phases of zeolite products

t Second Step
T First Step Hydrothermal
Phases
No.
Samples
(oC)
Hydrothermal (h)
1.
M1a
100
6
Ml, Q, H, Mt
2.
M1b
100
24
Ml, Q, H, Mt
3.
M1c
100
48
Ml, Q, H, Mt
4.
M1d
100
96
K-Cha, K-F, K-Phi, Ml, Q, H, Mt
5.
M2a
120
6
Ml, Q, H, Mt
6.
M2b
120
24
Ml, Q, H, Mt
7.
M2c
120
48
8.
M2d
120
96
K-Cha, K-F, K-Phi, Ml, Q, Mt
9.
M3a
150
6
Ml, Q, H, Mt
10.
M3b
150
24
Ml, Q, H, Mt
11.
M3c
150
48
12.
M3d
150
96
13.
M4a
180
6
Ml, Q, H, Mt
14.
M4b
180
24
15.
M4c
180
48
K-Cha, K-F, K-Phi, Ml, Q,H, Mt
16.
M4d
180
96
Mul=Mullite, Q=Quartz, H=Hercynite, Mag=Magnetite, K-Cha=K-Chabazite, K-F= K-F,
K-Phi=K-Phillipsite
Figure 1
Zeolite distribution at variation of first

step hydrothermal temperature 100, 120,
150 and 180oC: (a) K-Chabazite, (b) KPhillipsite, and (c) K-F. = 100oC; =
120oC; = 150oC; x = 180oC.
Proceeding Book
Types of zeolite from fly ash product similar

to zeolite that produced by Juan et al. (2007) at
variation of hydrothermal temperature. The
distribution is shown in Fig. 1. K-Chabazite
distribution can be seen at Fig. 1(a). At 100 oC, KChabazite formed after second hydrothermal time 48
hs. At 120 oC and 150 oC, this type zeolite formed
after 24 hs, but at 120 oC its compositions decreased
after 48 hs, while at 150 oC, its increased. At 180 oC,
K-Chabazite formed between 6 and 96 hs. The zeolite
compositions changes as shown at Fig. 1 due to phase
transformation of K-Chabazite phase into another
phase such as, K-Phillipsite and K-F. Distribution of
K-Phillipsite and K-F shown at Fig.1(a) and 1(c).
K-Phillipsite not formed until second
hydrothermal time 96 hs at 100 oC as shown at Fig.
1(b). At 120 oC and 150 oC, K-Phillipsite formed after
24 hs and its compositions increased until 96 hs. At
180 oC, K-Phillipsite formed after 6 hs and its
compositions increased until 48 hs, but after 48 hs its
decreased. The K-Phillipsite compositions decline
could be caused by redissolution of zeolite crystals
527

January 24, 2009
ISBN : 978 979 19201 0 0
and turn into another phase, such as K-F zeolite as

shown at Fig. 1 (c).
Fig. 1(c) described K-F zeolite distributions.
At 100 oC, K-F formed after second hydrothermal
temperature 48 hs. At 120 oC, 150 oC and 180 oC, K-F
formed after 24 hs and until 96 hs their compositions
increased, but after 48 hs K-F compositions at 180 oC
was the highest then its compositions at 120 oC and
150 oC.
Variation of first step hydrothermal
temperature as shown at Fig. 1 indicates a trend of
higher first step hydrothermal temperature shorter
zeolite crystallisation time. First step hydrothermal
process was process of dissolution of silicate,
aluminate and aluminosilicate species in fly ash.
Temperature influence in dissolution process based
on Kamali, et al. reports shows that Si concentration
in filtrate increase as temperature increase. While
Catalfamo, et al. (in Molina and Poole [12]) reported
that dissolution rate of aluminum goes faster than
Silicon dissolution at beginning of the process and its
concentration tends to increase as the temperature
increase. The higher silicate, aluminate, and
aluminosilicate concentrations in solution, the shorter
zeolite crystallisation rate. Bo and Hongzhu [3]
reported that higher temperature can promote
dissolution of the solid phase in the zeogel and
increases the concentration of the solution, thus
accelerating the formation of larger crystals and
decreasing the crystallization time. The temperature
was the main factor that affecting the type of
synthesized zeolite with KOH [10]. By applying
temperature in particular time intervals, one type of
zeolite phase transformed into another phase that
more stable, as the Ostwald_s rule; the first
polymorph of a compound formed from solution is
the least thermodynamically stable and is then
replaced in succession by more thermodynamically
stable polymorphs [1]. The changes of zeolite type at
variation of first step hydrothermal temperature
shown at Fig. 2.
Proceeding Book
Figure 2
The Changes of Zeolite Type at

Variation of First Step Hydrothermal
Temperature: a) 100oC, b) 120oC, c)
150oC, and d) 180oC.
= K-Chabazite; = K-Phillipsite, and *
= K-F.
The formed zeolites at 100 oC were KChabazite, K-Phillipsite, and K-F that formed
together after 48 hs. K-Chabazite at second
hydrothermal time 96 hs have highest composition
compared to K-Phillipsite and K-F compositions. At
120 oC, K-Chabazite, K-Phillipsite, and K-F were
formed together. Although those three zeolite types
formed togheter, but after 24 hs K-Phillipsite and K-F
compositions increased as second hydrothermal time
increased. K-Chabazite compositions also increased
after 24 hs but its compositions decreased after 48 hs.
At 150 oC, K-Chabazite, K-Phillipsite, and K-F also
formed together after 48 hs, but at 96 hs K-Chabazite
compositions were the highest of all zeolites. At 180
o
C after 6 hs, the three zeolite types, i. e K-Chabazite,
K-Phillipsite, and K-F formed together, but after 48
hs K-Chabazite and K-Phillipsite compositions
decreased while K-F compositions increased.
The variation of first step hydrothermal
temperature on zeolite synthesis from fly ash obtained
mixed three zeolite types, which there were
composition changes among formed zeolite phases.
These due to the zeolites may undergo different kinds
of structural changes including [5] : (i) cell volume
contraction due to the removal of water and/or
templating organic molecules (dehydration and
calcination); (ii) displacive or reconstructive phase
transformation(s) to more or less metastable phase(s);
(iii) breaking (and new formation) of TOT bonds;
(iv) negative thermal expansion (NTE); (v) structural
collapse; (vi) structural breakdown (i.e. complete
amorphization or recrystallization). Beside of
structural changes, the formation of mixed several
zeolite types due to the zeolites synthesized from fly
ash by direct conversion methods. Zeolite that
synthesized from fly ash by indirect conversion, such
as fusion methods or extractions could obtain single
phase zeolites [4,8].
Chemical compositions of zeolite from fly
ash were obtained from XRF measurement on sample
M4b and M4d as shown at Table 2. Chemical
compositions of zeolite from XRF analysis were
compared to calculated chemical composition from
quantitative XRD analysis.
Table 2 Chemical Compositions of Sample M4b and
M4d from XRF Analysis
% Weights
Components
M4b
M4d
Al2O3
29,20
26,70
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SiO2
K2O
Fe2O3
36,00
15,10
12,83
Chabazite, K-Phillipsite and K-F. Fe2O3 could be

found in Hercynite and Magnetite. The weight
percentage of those oxides was proportional to the
weight percentage of phases that contain those oxides.
Thus, the chemical compositions could explain the
zeolite quantities.
32,50
26,88
9,99
Al2O3 could be found in Mullite, Hercynite,

K-Chabazite, K-Phillipsite, and K-F. SiO2 could be
found in Mullite, Quartz, Hercynite, K-Chabazite, KPhillipsite, and K-F. K2O could be found in KTable 3 Mineral Compositions of Sample M4b and M4d
Mineral Phases
Compositions (%)
M4b
Quartz (SiO2)
Mullite (Al6Si2O13)
M4d
3,37
0,53
10,02
3,72
Magnetite (Fe3O4)
7,65
6,55
Hercynite (FeAl2O4)
0,02
0,00
22,97
0,39
K-Chabazite (K12(Al11Si25O72).40H2O)
K-Phillipsite (K10(Al10Si22O64).20H2O)
1,26
0,57
K-F (K10(Al10Si10O40).8H2O)
0,73
30,77
53,98
57,47
Amorphous
Al2O3, K2O, and Fe2O3 that contained in unidentified

Based on Table 3, SiO2 contents in sample
M4b were 17,39% and in sample M4d were 12,74 %.
phases by XRD methods. Besides, those oxides could
Al2O3 contents in sample M4b were 23,05 % and in
be in amorphous phases that have high contents, i. e
53,98 % in sample M4b and 57,47 % in sample M4d.
sampel M4d were 23,89 %. K2O contents in sample
CEC measurement of zeolite from fly ash
M4b were 8,77 %, while in sample M4d were 20,50
was conducted only to sample M1d, M2d, and M4d
%. Fe2O3 contents in sample M4b were 15,29 % and
because of sample availability. Zeolite phase
in sample M4d were 13,08 %.
compositions calculated and measured CEC results
SiO2, Al2O3, K2O, and Fe2O3 contents in
shown in Table 4.
sample M4b and M4d in Table 3 different from XRF
results in Table 2. These due to the existence of SiO2,
Table 4 Zeolite Phase Compositions, Calculated and Measured CEC Results.
Zeolite Phase Compositions (%)
Samples
Calculated CEC (meq/g)
Measured CEC (meq/g)
K-Cha
K-Phi
K-F
M1d
47,40
0,03
1,24
1,778
2,304
M2d
2,90
3,33
19,44
1,360
2,509
M4d
0,39
0,57
30,77
1,819
3,091
The differences between calculated and

measured CEC might be caused by the existence of
nonzeolitic phases that have ability to exchange
cations. Those phases may be contained in
unconverted phases of fly ash. Hidayati, et al.[7]
reported that CEC measured of the fly ash were 4,46
meq/100 g fly ashes. This result indicates that there
are phases in fly ash that able to exchange cations.
Conclusions
Proceeding Book
From the discussions above, it is concluded that the

higher the first step hydrothermal temperature on
synthesis of zeolite from fly ash, the shorter the
second hydrothermal reaction needed for zeolite
crystallisation. Different compositions of three mixed
zeolite phases, i.e K-Chabazite, K-Phillipsite, and KF formed at variation of first hydrothermal
temperature (100, 120, 150 and 180oC) during second
hydrothermal time 6-96 hs on synthesis of zeolite
from fly ash.
Calculated weight percentage of oxide of
zeolites in this study different from XRF result due to
529

January 24, 2009
ISBN : 978 979 19201 0 0
the existences of oxides in unidentified phases and

amorphous phases, then could not be quantified by
Rietveld method. The differences between calculated
CEC and experiment were caused by exchangeable
cations of nonzeolitic and amorphous phases.
Acknowledgements
The authors would like to thank Mr. Suminar Pratapa
from Physics Department, ITS Surabaya for his help
on part of the XRD data collection and analyses.
Funding for this research was provided by grant from
The Ministry of Research and Technology, Republic
of Indonesia.
References
[1] Barrer, R. M. 1982. Hydrothermal chemsitry of
zeolites. London: Academic Press.
[2] Berkgaut, V.& Singer, A. 1996. High capacity
cation
exchanger
by
hydrothermal
zeolitization of coal fly ash. Applied Clay
Science 10: 369-378.
[3] Bo, W. & Hongzhu, M. 1998. Factors affecting
the synthesis of microsized NaY zeolite.
Microporous and Mesoporous Materials 25:
131136.
[4] Chang, H., & Shih, W. 1998. Conversion of fly
ash into zeolites for ion-exchange
applications. Materials Letters 28: 263-268.
[5] Cruciani, G. 2006. Zeolites upon heating: factors
governing their thermal stability and
structural changes. Journal of Physics and
Chemistry of Solids 67: 19731994.
[6] El-Naggar, M.R., El-Kamash, A.M., El-Dessouky,
M.I., Ghonaim A.K. 2008. Two-step method
for preparation of Na-X zeolite blend from
fly ash for removal of Cesium ions. Journal
of Hazardous Materials 154: 963972.
[7] Hidayati, R.H. 2008. Sintesis zeolit dari abu
layang batubara: kajian pengaruh waktu
hidrotermal awal terhadap pembentukan
zeolit. Tesis tidak diterbitkan Institut
Teknologi Sepuluh November Surabaya.
[8] Hollman, G.G., Steenbruggen, JanssenJurkovicvova M. 1999. A two-step process
for the synthesis of zeolites from coal fly
ash. Fuel 78: 12251230.
[9] Hui, K.S. & Chao, C.Y.H. 2006. Effects of stepchange of synthesis temperature on synthesis
of zeolite 4A from coal fly ash. Microporous
and Mesoporous Materials 881: 45151.
[10] Juan, R., Hernandez, S., Andres, J. M., Ruiz, C.
2007. Synthesis of granular zeolitic materials
with high cation exchange capacity from
Proceeding Book
agglomerated coal fly ash. Fuel 86:1811

1821.
[11] Kamali, M., Vaezifar, S., Kolahduzan, H.,
Malekpour, A., Abdi, M. R. 2008. Synthesis
of nanozeolite a from natural clinoptilolite
and aluminum sulfate: optimization of the
method. Powder Technology, Article in
Press.
[12] Molina, A. & Poole, C. 2004. A comparative
study using two methods to produce zeolites
from fly ash. Minerals Engineering 17: 167
173.
[13] Muasyaroh, D., Prasetyoko, D., Fansuri, H.
2007. Pengaruh waktu hidrotermal terhadap
pembentukan zeolit dari fly ash batu bara.
Prosiding, Seminar Nasional Kimia Jurusan
Pendidikan Kimia FMIPA Universitas
Negeri Yogyakarta, 17 November 2007.
[14] Murayama, N., Takahashi, T., Shuku, K., Lee,
H., Shibata, J. 2008. Effect of reaction
temperature on hydrothermal syntheses of
potassium type zeolites from coal fly ash.
Int. J. Miner. Process., Article in Press.
[15] Querol, X., Alastuey, A. S., Lopez-Soler, A.,
Plana, F. 1997. A fast method for recycling
fly ash: microwave-assisted zeolite synthesis.
Environ. Sci. Technol. 31: 2527-2533.
[16] Querol, X., Umana, J.C., Plana F., Alastuey, A.,
Lopez-Soler, A., Medinaceli, A., Valero, A.,
Domingo, M. J., Garcia-Rojo, E. 2001.
Synthesis of zeolites from fly ash at pilot
plant
scale.
example
of
potential
applications. Fuel 80: 857-865.
[17] Shigemoto, N., Hayashi, H., Miyaura, K. 1993.
Selective formation of Na-X, zeolite from
coal fly ash by fusion with sodium hydroxide
prior to hydrothermal reaction. J. Mater. Sci.
28: 4781 4786.
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NOx Adsorption with CuO Supported on NaY Zeolite from Rice Husk
Chusnul Suraidah, Irmina Kris Murwani*
Chemistry Departement, Faculty of Mathematics and Natural Sciences
Institut Teknologi Sepuluh Nopember
Kampus ITS Sukolilo, Surabaya, Indonesia
*
e-mail : irmina@chem.its.ac.id
Abstract
NOx adsorption has been studied on NaY zeolite and CuO (5, 10 and 15% wt) supported on NaY zeolite
(CuO/NaY) from rice husk. NaY and CuO/NaY were characterized using XRD, FT-IR and spesific
surface area were determined by methylene blue method. The spesific surface area of NaY, 5% CuO/NaY,
10% CuO/NaY and 15% CuO/NaY are 8,130; 8,127; 8,124 and 8,121 m2/g respectively. After adsorption,
the NOx concentration on adsorbent was determined by colorimetry method. Adsorptivity of NOx
adsorbent from higher to lower are 5% CuO/NaY > 10% CuO/NaY > 15% CuO/NaY > NaY. This result
are proportional with spesific surface area and reverse with adsorbent acidity for CuO/NaY zeolite.
Adsorptivity was influenced by active adsorbent sites.
Keywords: NaY and CuO/NaY synthesis, NOx adsorption, colorimetry.
Introduction
Thus, rice husk garbage was hoped useful and NOx

can reducible.
Experiment about nitrogen oxides (NOx) has been

studied before because NOx are important family of
air polluting chemical. NOx sources produced from
chemistry reaction, combustion, automobiles and
industrial. NOx are extremely toxic, it can made
ozone in the air, lung diseases such asthma and acid
rain [15]. Adsorption principle can used to solve this
problem, adsorbent was used to NOx adsorption. NOx
adsorption with zeolite and Al2O3 adsorbent has been
studied before [1,2,12]. Zeolite synthesis has been
done from rice husk as silica source [10].
Hydrothermal method was used to NaY zeolite
synthesis with comparison specific composition [13].
High sillica content (94-96%) in rice husk to enable
zeolite was synthezed from this material [6,17]. Ba,
Pt and MnO2 supported on NaY zeolite was used as
adsorbent, present metal loading in zeolite shown
adsorptivity zeolite increase [1,5,9].
Indonesia as producer rice plant yield rice husk
garbage, for that reason benefit of rice husk must be
looking. High silica content in rice husk can used as
silica precursor in zeolite synthesis that used as
adsorbent. On the other hand, increasingly industrial
and automobiles make NOx emission increase. Based
on two problem above, experiment zeolite synthesis
from rice husk must be done and than zeolite used as
NOx adsorbent. Metal supported on zeolite can
increase adsorptivity, so that CuO supported on
zeolite NaY from rice husk must be studied too.
Proceeding Book
Preparation Adsorbent
In this research, SiO2 precursor for synthesis of NaY
was taked from rice husk. NaY zeolite synthesis was
performed according to composition of 10 Na2O :
Al2O3 : 15 SiO2 : 300 H2O (molar ratio). The initial
precursor was prepared by mixing aluminate gel and
silicate gel. After that, the mixture was heated in an
oven at 100C for 24 hour. Subsequenly, the solid
product was separated by filtration, washed and dried
for overnight. CuO/NaY zeolite synthesis was
prepared by incipient wetness impregnation with CuO
prosentage 5,10 and 15%. The mixture was dried at
temperature 100C. The calcination of the prepared
samples was performed in air at 400C for 4 hour.
Characterization
Adsorbent characterization was carried out by means
of XRD and FTIR. XRD characterization was
performed using XRD JEOL JDX 3530 (Cu)
equipment. FTIR characterisation was performed
using FTIR Shimadzu 8201 P equipment. The
specific surface area of adsorbent was determined by
methylene blue method. Adsorbent acidity was
analysed by FT-IR after pyridine adsorption
(pyridine-FTIR).
531

January 24, 2009
ISBN : 978 979 19201 0 0
3000
2000
1000
0
10
40
50
60
70
80
90
Figure 1. XRD pattern of NaY zeolite

90
%T
60
TO
TO
4000
3000
2000
574
503
HOH
30
OH
Proceeding Book
30
2 ( )
1000
1/cm
Figure 2. FT-IR spectra of NaY zeolite
Intensitas (cps)
The XRD pattern of NaY zeolite, shown in Fig. 1.

The diffraction lines characteristic of NaY at 2 : 6,
10, 12, 15 dan 24 [PPIT FAU (Powder Pattern
Identification Tabel Faujasite)]. The framework IR
spectra of NaY zeolite, shown in Fig. 2. The bands at
about 3450 cm-1 was caused by vibrations of O-H and
HO-H which are the consequence of the adsorption of
water. The presence of water was also evidenced by
the H-O-H band at 1633 cm-1. The bands at about
1116 cm-1, 955 cm-1, 774 cm-1, 714 cm-1 are due to
symmetric and asymmetric stretching mode of
(Si,Al)O4 tetrahedra. The bands at about 574 cm-1,
503 cm-1 are due to vibration related to external
linkages of double ring polyhedra in the zeolite
framework [7, 13, 16].
CuO/NaY zeolite was synthezed by the incipient
wetness impregnation with 5, 10 and 15% of Cu
loadings. The XRD pattern of NaY and CuO/NaY,
shown in Fig. 3. The XRD pattern of CuO/NaY show
evidence of CuO phase at 2 : 35; 38 dan 48 that
labeled with (*) [3]. The framework IR spectra of
CuO/NaY zeolite, shown in Fig. 4. The bands at
about 3450 cm-1, 1633 cm-1 are caused by vibrations
of O-H and HO-H, bending vibration of H-O-H,
respectively. The bands at about 1116 cm-1, 955 cm-1,
774 cm-1, 714 cm-1, 574 cm-1, 503 cm-1 are typical for
NaY [7 13, 16]. The bands at about 1396 cm-1, 567
cm-1 dan 458 cm-1 due to CuO [3].
20
TO
TO
The adsorptivity of solids product NaY and

CuO/NaY were tested by adsorption of NOx onto
adsorbent samples, extraction of NOx from the
occluded samples using a solvent, reduction of
nitrogen oxides to nitrite ions contained in the extract
using hydrazine sulfate and detection and
quantification of nitrogen oxides by colorization
using a modified Griess reagent [8, 11].
Intensitas (cps)
NOx adsorption test
(b )
(a)
10
20
30
40
50
60
70
80
2 ()
Figure 3. XRD pattern of NaY (a) and CuO/NaY(b)
532
90

January 24, 2009
ISBN : 978 979 19201 0 0
with adsorbent acidity for CuO/NaY zeolite. NOx was

adsorpted on cation, oxygen atoms and hydroxyl
groups, that are active zeolite sites [1,2,4,9,12]. NOx
adsorption on CuO/NaY zeolite was not influenced
presence Cu2+ because this cation has been
surrounded by oxygen atoms. This indicate that
adsorptivity was influenced active adsorbent sites.
(d)
(c)
(b)
(a)
CuO
1000
1/cm
Figure 4. FT-IR spectra of NaY (a) and CuO/NaY

(5% CuO/NaY (b), 10% CuO/NaY (c), 15%
CuO/NaY (d))
Specific surface area measured by methylene blue
method. Surface area of NaY, 15% CuO/NaY, 10%
CuO/NaY and 5% CuO/NaY are 8,130; 8,121; 8,124
and 8,127 m2/gram, respectively.
FTIR spectra of pyridine adsorbed on NaY and (5,
10 and 15%) CuO/NaY are shown in Fig. 5. The
vibration bands at about 1450 cm-1, 1490 cm-1 and
1610 cm-1 correspond to pyridine coordinated on
Lewis acid sites that labeled with (*) [14]. Adsorbent
acidity from higher to lower are 15% CuO/NaY >
10% CuO/NaY > 5% CuO/NaY > NaY.
*
(a)
NOx (mmol)
2000
0.3
T-O
T-O
T-O
3000
T-O
HOH
HO
4000
CuO
CuO
0.4
0.2
0.1
0.0
NaY
5% CuO/NaY
10% CuO/NaY
15% CuO/NaY
Adsorbent
Figure 6. NOx adsorption test on adsorbent NaY and

CuO/NaY.
Conclusion
Adsorptivity of zeolite increase after CuO
supported on NaY zeolite. Adsorptivity of NOx
adsorbent from higher to lower are 5% CuO/NaY >
10% CuO/NaY > 15% CuO/NaY > NaY.
Adsorptivity was influenced by active adsorbent sites
and surface area, but was not influenced adsorbent
acidity.
*
(b)
Acknowledgements
(c)
*
*
(d)
1800
1700
1600
1500
1400
1300
This reasearch was supported by Chemistry

Departement, Faculty of Mathematics and Natural
Sciences, Institut Teknologi Sepuluh Nopember
Surabaya. The autors thanks LPPM ITS for their
financial support.
-1
1/ (cm )
Figure 5. FT-IR spectra of NaY (a) and CuO/NaY

(5% CuO/NaY (b), 10% CuO/NaY (c), 15%
CuO/NaY (d)) after pyridine adsorbed.
The result of NOx adsorption test on NaY and (5,
10, 15%) CuO/NaY adsorbent shown in Fig. 6.
Adsorptivity of CuO/NaY zeolite was higher than
NaY zeolite, it caused presence CuO in NaY zeolite.
Adsorptivity of 5% CuO loading was higher than
15% CuO loading. Adsorptivity decrease with
increasingly CuO loading on NaY zeolite, because
CuO cover zeolite surface. This results are
proportional with spesific surface area and reverse
Proceeding Book
References
[1]
[2]
[3]
[4]
Bentrup, Ursula., Angelika Brckner, Manfred

Richter, Rolf Fricke, Applied Catalysis B:
Environmental 32, (2001), 229241.
Brosius, Roald., Kalle Arve, Marijke H.
Groothaert, Johan A. Martens, Journal of
Catalysis 231, (2005), 344353.
El-Bahy, Zeinhom Mohamed., Materials
Research Bulletin, (2007).
Gil, Barbara., Karolina Mierzynska, Monika
Szczerbinska, Jerzy Datka, Applied Catalysis
A: General 319, (2007), 6471.
533

January 24, 2009
ISBN : 978 979 19201 0 0
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
Goscianska, Joanna., Philippe Bazin, Olivier

Marie, Marco Daturi, Izabela Sobczak, Maria
Ziolek, Catalysis Today 119, (2007), 7882.
Harsono, heru., Jurnal Ilmu Dasar vol. 3, No.
2, (2002), 98-103.
Holmberg, Brett A., Huanting Wang, Yushan
Yan, Microporous and Mesoporous Materials
74, (2004), 189198.
Kil, Jeong Ki., In Sik Nam, Joo-Hyoung Park,
Sang Jun Park, United States Patent
Application Publication, US 2006/0024836
A1, (2006).
Li, Gonghu., Conrad A. Jones, Vicki H.
Grassian, Sarah C. Larsen, Journal of Catalysis
234,(2005), 401413.
Malek, Nik Ahmad Nizam Nik., Alias Mohd
Yusof, The Malaysian Journal of Analytical
Sciences, Vol 11, No 1, (2007), 76-83.
Park, Joo-Hyoung., Min S. H., Sang J. P., Sang
j. P., et all, Journal of Catalysis 241, (2006),
470-474.
Perdana, Indra, , Derek Creasera,, I. Made
Bendiyasab, Rochmadib, BomaWikan Tyosob,
Chemical Engineering Science 62, (2007),
3882 3893.
Sang, Shiyun., Zhongmin Liu, Peng Tian, Ziyu
Liu, Lihong Qu, Yangyang Zhang, Materials
letters 60, (2006), 1131-1133.
Salama, Tarek M., Ayman H. Ahmed, Zeinhom
M. El-Bahy, Microporous and Mesoporous
Materials 89, (2006), 251259.
Velsen, Daniel Van., Sulphur Dioxide and
NitroOxides in ndustrial Waste Gases:
Emission, Legislation and Abatement, Kluwer
Academic Publishers, Netherlands, (1991).
Weitkamp, J., L. Puppe, Catalysis and Zeolites
Fundamental and Application, Springer, New
York, (1999).
Yalcin, N., V. Sevinc, Ceramic International 27,
(2001), 219-224.
Proceeding Book
534

January 24, 2009
ISBN : 978 979 19201 0 0
NOx Adsorption with Cr Supported on NaY Zeolite from Rice Husk

Adhita Febriana and Irmina Kris Murwani
Chemistry Study Program, Faculty of Mathematics and Natural Sciences
Sepuluh Nopember Institute of Technology Surabaya,
Keputih Sukolilo, Surabaya, Indonesia, 60111.
*Email : irmina@chem.its.ac.id
Abstract
NOx adsorption with Cr supported on NaY zeolite from rice husk have been investigated. The
adsorbent used in this studied were NaY zeolite and Cr2O3/NaY that made from rice husk. Rice husk
was used for precursor NaY zeolite because its has high content SiO2 about 94 96%. Cr2O3/NaY
(2,97 and 3,84 wt%) were synthesized by impregnation method. The adsorbents were characterized
by XRD, FTIR, the specific surface areas was determined by the methylene blue method and the
acidity was carried out by pyridine FTIR. The concentration of NOx gas was analyzed with
colorimetric method. The adsorptivity for NOx gas decreased in the order Cr2O3/NaY 3,84% >
Cr2O3/NaY 2,97% > zeolit NaY. The specific surface areas of NaY zeolite was 8,1301 m2/g,
Cr2O3/NaY 2,97% was 8,1301 m2/g, and Cr2O3/NaY 3,84% was 8,1048 m2/g.
Keywords: Adsorption NOx gas, NaY, Cr2O3/NaY, rice husk
Introduction
zeolite with metal shows the influence of increasing

the capacity of adsorption.
Generally, chemical reactions will produce side

products that often become waste, where the waste
will become a new problem because it will
contaminate the surrounding environment. One of
the side products of the chemical reaction is
nitrogen oxide gas (NOx), which is one of the side
products of the synthesis of picric acid. Generally,
the NOx gas is a chemical compound derived from
burning coal or petroleum, generated from the
disposal automobile and machine. NOx gas is one
of the air pollutant that is quite dangerous for the
environment because the NOx gas can cause
damage to people, such as emphysema and lung
damage, and will also damage the ozone, which is a
major cause of global warming and acid rain.
Therefore, need to be a way to the NOx gas in the
air can be reduce (Kil, 2006; Sakamoto, 2006).
One way to reduce NOx gases in the air is
adsorption the NOx gases with an adsorbent.
Materials that can be used as adsorbent is Al2O3,
MgF2, zeolite and many more other materials that
can be used as adsorbent. Synthesis of zeolite has
been done by many researchers on the previous
investigation including Sang (2005), Malek (2007),
and Gonghu Li (2005) by using several methods
and comparison mol certain. One way to get zeolite
is from rice husk because SiO2 content on rice husk
is high (94 - 96%) allows zeolite can be synthesis
from these raw materials. Zeolite containing metal
such as Mn, Mo, Pt, Pd and Ba have also been
made by previous researchers, where loading
Rice is the main agricultural products in the

agricultural countries, including Indonesia. This is
because rice is one of the staple food in Indonesia.
Rice husk is one of the side products of rice milling
process, which until the current rice husk is waste
that still has not been used optimally. During this
rice husk is only used as a propellant brick or just
casually discarded. Some research indicates that
rice husk ash have the silica content is high enough,
where silica is one of the basic materials for
synthesis of zeolite (Harsono, 2002; Malek, 2007).
During this research about adsorption of NOx
gas is very low, which zeolite used as support for
adsorption of NOx gas. In order for the utilization
of waste rice husk as a producer of silica for
synthesis zeolite and in order to overcome the air
pollution in the NOx gas, so need research on the
NOx gases adsorption on zeolite NaY and
Cr2O3/NaY made from rice husk. This research
started from preparation source of silica from rice
husk and synthesis zeolite NaY. Then zeolite NaY
will impregnation with CrCl36H2O that will be
obtained Cr2O3/NaY, where zeolite NaY and
Cr2O3/NaY is then tested with XRD, FT-IR, with a
surface area of the measurement method methylene
blue and test the acidity with pyridine-FTIR. In
addition, the test adsorption of zeolite NaY and
Cr2O3/NaY will be done by conducting NOx gas at
adsorbent and analyzed by colorimetric method to
know the concentration of NOx gases.
Proceeding Book
535

January 24, 2009
ISBN : 978 979 19201 0 0
Preparation of adsorbents
In this research, SiO2 precursor for synthesis of
NaY zeolite was taked from rice husk. Synthesis
NaY zeolite was performed according to the
composition of 10 Na2O : Al2O3 : 15 SiO2 : 300
H2O (molar ratio) [12]. The initial precursor was
prepared by mixing the required amounts of
aluminat gel solution and silicate gel, stirred for
two hours, and then heated at the temperatures of
100C for 12 hours. The results of synthesis then
filtered, washed, and dried in an oven at the
temperatures of 100C for 24 hours so it will be
acquired zeolite NaY. The adsorbents of 2,97 and
3,84 wt% Cr2O3/NaY were prepared by
impregnation method using CrCl36H2O solution.
The adsorbents were dried at 100C for 24 hours
and calcined in air at 400C for 4 hours [14].
H2O (Sang, 2005). Synthesis of zeolite NaY will

also be performed on hidrotermal assisted with the
high temperatures with the water.
The solvent of silicate gel and aluminat are
mixed, and then inserted into the reactor and
heated at the temperatures of 100C for 12 hours.
After cold, the mixture is filtered and washed with
aquades up to its neutral pH (Prasetyoko, 2005;
Sang, 2006). The solid that have been obtained,
then dried in the oven for 24 hours at the
temperature of 100C so it will be obtained powder
of zeolite NaY is creamy. Powder of zeolite NaY
is then characterized with XRD, as seen in the
Figure 2.
Intensitas (cps)
Characterization
Adsorption of NOx Gas on Zeolite NaY and

Cr2O3/NaY from Rice Husk
PPIT
20
80
NaY
2500
2000
1500
1000
T - O ulur
3000
Cincin ganda
3500
TO4 eksternal
4000
TO4 internal
O-H
Proceeding Book
2 ()
60
Figure 1. Pattern of Zeolit NaY

Pattern of zeolite NaY showed the peak in the
region 2 about 6, 10, 12, 15 and 24, which where
area in the region 2 about 6 with the highest
intensity shows typical peak of zeolite NaY. This is
in accordance with the peaks on the standard PPIT
(Powder Pattern Identification Table), so this shows
that the synthesis of zeolite NaY has been
successful.
In addition analyzed with XRD, zeolite NaY
also analyzed by FTIR. In the figure 3, there is a
peaks in the region 3,450 cm-1 shows the region of
O-H vibration stretching associated with water. At
the peak of 1633 cm-1 shows the peak for H-O-H.
Peak area in 1116 cm-1 shows the peak of TO4
asimetri external linkages vibration stretching (T =
Si or Al) (Prasetyoko, 2005).

Synthesis of zeolite NaY begins with preparation
of SiO2 obtained from rice husk ash. Zeolite NaY
is synthesized from silicate gel and aluminat with
the comparison 10 Na2O : Al2O3 : 15 SiO2 : 300
40
H-O-H
Adsorption involves the uptake NOx gas by the

adsorbents. The tube contains about 20 mg of
adsorbent were placed in the reactor adsorption.
The sample were activated by heating to 100C and
then NOx gas was adsorbed for 1 hour at room
temperature. All the adsorbents were extracted at 5
times. About 15 mL aquades was added to each
adsorbents, and then sentrifuge for 15 minutes. One
mL CuSO4 solution, 1 mL hidrazine sulphate
solution and 2 mL sodium hydroxide solution were
added per 1 mL of eluted solvent. Reduction was
performed at 40C for 15 minutes, and then the
chemical sensor was the Griess reagent, containing
N-1-naphthylethylenediamine
dihydrochloride
(NED) dissolved in 85% phosphate solution
containing 1 g of sulphanyl amide, then diluted to
100 mL was added. The changes color then
measured with spectrophotometer on the
wavelength 540 nm [2,4,9].
Zeolit NaY
T (%)
Adsorbents characterization was carried out by

means of XRD and FTIR. XRD characterization
was performed using XRD JEOL JDX 3530 (Cu
K) equipment. FTIR characterization was
performed using Shimadzu FTIR 8400S equipment.
Specific surface areas were determined by
methylene blue method. Lewis acid sites and
Brnsted acid were analyzed by pyridine FTIR.
500
1/cm
Figure 2. Spectra FTIR of Zeolit NaY
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January 24, 2009
ISBN : 978 979 19201 0 0
Intensitas (cps)
Cr2O3/NaY
Cr2O3
20
40
2 ()
60
80
Figure 3. Patterm of Zeolite NaY, Cr2O3/NaY and

Cr2O3
In the figure 4, the pattern of impregnation is
not shows the significant changes of the pattern of
zeolite NaY. There are differences in the intensity
both of the pattern where the intensity of
Cr2O3/NaY () is lower than zeolite NaY. This
shows that zeolite NaY has been impregnated with
Cr2O3, but because the percentage of loading of
ion Cr3+ is small, the peak of Cr2O3 (*) does not
appear, but will only reduce the intensity of the
supported of zeolite NaY. From the pattern can
also be known that impregnation is not damage the
structure of supported zeolite NaY, although the
intensity is reduced when compared with pattern of
supported zeolite NaY. Cr2O3/NaY which has been
obtained, besides characterized with XRD also
analyzed by FTIR.
Proceeding Book
T (%)
4000
3500
3000
2500
2000
1500
TO4
5+
Cr = O
H-O-H
Zeolit NaY
In the figure 4 shows that peak intensity at

3,492 cm-1 shows the region O-H vibration
stretching associated with water. Peak at 1641 cm-1
shows region of the H-O-H (Liu, 2003). Peak in
2071 cm-1 () shows the intensity decreased from
zeolite NaY > Cr2O3/NaY 2,97% > Cr2O3/NaY
3,8%. This is because this area is a likely peak of
the T-O-H (T = Al or Si), where the H atoms in the
T-O-H will be replaced with ion Cr3+, which are
absorbed into the Zeolite NaY when impregnation.
Because not all H atoms can be replaced by ion
Cr3+, the peak intensity in the region in 2071 cm-1
will not lost all.
O-H
At the peak of 955 cm-1 shows the region to

TO4 tetrahedron asimetri internal vibration
stretching (Liu, 2003) and can also indicate areas
vibration stretching (alumino) of silicate and silica
polimorfis. Peak in the 774 and 714 cm-1 is the
peak symmetry vibration stretching T-O. Peak in
the 578 and 503 cm-1 which does not show sharp
regional for a double ring of the external linkages
related to the structure of the framework Zeolite
NaY (El - Bahy, 2007; Sang, 2006; Weitkamp,
1999).
After synthesis of zeolite NaY as supported
have been successful, this research followed by
metal loading CrCl36H2O on supported zeolite
NaY through impregnation. The impregnation
method used is the incipient wetness method.
Impregnation will done by mixed the powder
zeolite NaY in solution CrCl36H2O with a
percentage loading are 2.97 and 3.84%. Mixed in
the form of pulp is then dried at temperatures of
100C for 24 hours and calcined at the
temperatures of 400C for four hours for activation
adsorbent with the purpose to remove the solvent
(Weitkamp, 1999). The powder are obtained after
calcinations are a bright yellow powder and then
characterized with XRD. The pattern of the
analysis as shown in figure 4.
1000
500
1/cm
Figure 4. Spectra FTIR of (a) Zeolit NaY,

(b) Cr2O3/NaY 2,97%, (c) Cr2O3/NaY
3,84%
Two peaks in 1478 and 1423 cm-1 on zeolite
NaY ( ) after becoming lost when zeolite NaY
impregnation with Cr3+, but this peak can not be
characterized. Peak area in 1179 cm-1 shows the
structure of chromium where this is related to Cr5 +
= O (Wojciechowska, 1995). At the peak of 797cm1
shows the region to TO4 tetrahedron external
symmetry vibration stretching (Liu, 2003) and can
also indicate areas vibration stretching of
tetrahedral symmetry SiO4 (Prasetyoko, 2005).
Peak 955 cm-1 shows vibration stretching that TO4
tetrahedron asimetri internal (Liu, 2003) and
vibration stretching (alumino) silicate and silica
polimorfis.
In this research, the specific surface area of the
determination made by using the methylene blue
method. This method begins with the determination
of the maximum length of the wave and making the
calibration curve to know the concentration of
methylene blue absorbed by the sample so that the
specific surface area of each sample can be
calculated. The result as shown in table 1.
Table 1. Surface Area Adsorbent
Adsorbent
Zeolite NaY
Cr2O3/NaY 2,97%
Cr2O3/NaY 3,84%
Spesific Surface Area

(m2/g)
8,1301
8,1301
8,1048
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January 24, 2009
ISBN : 978 979 19201 0 0
Adsorbent which has been obtained in this

research is then used to adsorption of NOx gas with
the ability to see how the adsorptivity from each
adsorbent. The results of adsorption test for each
adsorbent as the following:
Conclusion
0.40
Acknowledgements
0.35
The authors are grateful to the Chemistry

Departement, all the participant that help make this
research, and the financial support from The
Ministry of National Education.
NOx (mmol)
0.30
0.25
0.20
0.15
0.10
References
0.05
0.00
NaY
Cr2O3/NaY 2,97%
Cr2O3/NaY 3,8%
Figure 5. Relations between the adsorbent with the

amount of gas absorbed NOx
On the figure 6, adsorbent shows that most
high adsorptivity is Cr2O3/NaY 3.84% at 0.39
mmol. Adsorptivity adsorbent sequence from the
largest to the smallest is Cr2O3/NaY 3.84% >
Cr2O3/NaY 2.97% > zeolite NaY. Adsorbent with
a specific surface area is large that is expected to
have a high adsorptivity, but the adsorptivity from
the adsorbent is not influenced by the specific
surface area and acidity, but more influenced by
the distribution of ion Cr3+. This can be seen from
the surface area of the order of the adsorbent :
zeolite NaY = Cr2O3/NaY 2.97% > Cr2O3/NaY
3.84%. From the spesific surface area that zeolite
NaY and Cr2O3/NaY 2.97% have large surface
area but the adsorptivity smaller when compared
with Cr2O3/NaY 3.84%, which has a surface area
of the smallest but have the highest adsorptivity if
compared with the other adsorbent. This indicates
that the specific area of the adsorbent not affect
adsorptivity.
In terms of acidity, the nature acidity of
Cr2O3/NaY 2,97% and 3,84% is Brnsted acid. On
the other side, zeolite NaY is Lewis acid. From the
data specific surface area and acidity of the each
adsorbent, the adsorptivity from the adsorbent is
not influenced by the specific surface area and the
acidity, but more influenced by the distribution of
ion Cr3+. The adsorbent Cr2O3/NaY 3.84% has ion
Cr3+ more on the surface if compared with other
adsorbent, so the adsorptivity of Cr2O3/NaY 3.84%
will have the highest if compared with the other
adsorbent. This is in accordance with the results of
the test adsorption of NOx gas that has been done,
where the NOx gas will be attached to the surface
Cr2O3 in the form of [-O-N = O +], where N atoms
that has positive charge will be attached to the O
atoms in the Cr2O3 so a lot of Cr2O3 that are
absorbed and stick on zeolite NaY surface, the NOx
gas that adsorp on the adsorbent will be higher.
Proceeding Book
[1]El - Bahy, Z. H., (2007), Oxidation of Carbon

Monoxide over Cu- and Ag-NaY Catalysts
with Aqueous Hydrogen Peroxide, Materials
Research Bulletin.
[2]Haris, Daniel C., (1997), Exploring Chemical
Analysis, New York : W. H. Freeman and
Company.
[3]Harsono, Heru, (2002), Pembuatan Silika
Amorf dari Limbah Sekam Padi, Jurnal Ilmu
Dasar, Vol. 3, No. 2, hal. 98 103.
[4]Kil, J. K., Nam, I. S., Park, J. H., Park, S. J.,
(2006), Quantitative Analysis of Nitrogen
Oxides Occluded in Heterogeneous Catalysis,
Patent Application Publication, Pub. No. US
2006/0024836 A1.
[5]Li, G., Jones, C. A., Grassian, V. H., Larsen, S.

C., (2005), Selective Catalytic Reduction of
NO2 with Urea in Nanocrystalline NaY
Zeolite, Journal of Catalysis, 234, hal. 401
413.
[6]Liu, X., Yan, Z., Wang, H., Luo, Y., (2003), In
situ Synthesis of NaY Zeolite with CoalBased Kaolin, Journal of Natural Gas
Chemistry, 12, hal. 63-70.
[7]Malek, N. A. N. N., Yusof, A. M., (2007),
Removal of Cr(III) From Aqueous Solutions
Using Zeolite NaY Prepared From Rice Husk
Ash, The Malaysian Journal of Analytical
Sciences, Vol. 11, No. 1, hal. 76 83.
[8]Nakamoto Kazuo. 1978. Infrared and Raman
Spectra of Inorganic and Coordination
Compounds. Third edition. America : John
Wiley & Sons.
[9]Park, Joo-Hyoung., Han, M. S., Park, S. J.,
Kim, D. H., Nam, In-Sik, Yeo, G. K., Kil, J.
K., Youn, Y. K., (2006), Colorimetric Assay
for a Fast Parallel Screening of NOx Storage,
Journal of Catalysis, 241, hal. 470 474.
[10] Prasetyoko, D., Ramli, Z., Endud, S.,
Hamdan, H., Silikowski, B. (2005),
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Conversion of Rice Husk Ash to Zeolite

Beta, Waste Management.
[11] Sakamoto, Y., Okumura, K., Kizaki, Y.,
Matsunaga, S., Takahashi, N., Shinjoh, H.,
(2006), Adsorption and Desorption Analysis
of NOx and SOx on a Pt/Ba Thin Film Model
Catalyst, Journal of Catalysis, 238, hal. 361
368.
[12] Sang, S., Liu, Z., Tian, P., Liu, Z., Qu, L.,
Zhang, Y., (2006), Synthesis of Small
Crystals Zeolite NaY, Materials Letters, 60,
hal. 1131 1133.
[13]
Weitkamp, J and Puppe, L. 1994. Catalysis and Zeolites

Fundamentals an Aplications. Springer.
[14] Wojciechowska,
M.,
Zielinski,
M.,
Przystajko, W., Pietrowski, M., (2007), NO
Decomposition and Reduction by C3H6 Over
Transition Metal Oxides Supported on MgF2,
Catalysis Today, 119, hal. 44 47
[15] Yalin, N., Sevin, V., (2001), Studies on
Silica obtained from Rice Husk, Ceramics
International, 27, hal. 219 224.
Proceeding Book
539

January 24, 2009
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Synthesis of Calcium Phosphate Carbonate-Polyglycolide Composite using

Precipitation Method
Kiagus Dahlan, Arif Rahmadi, Yessie Widya Sari
Department of Physics, Faculty of Mathematics and Natural Sciences, Institut Pertanian Bogor,
Jalan Meranti, Kampus IPB Dramaga, Bogor, Indonesia
Abstract
Composite of calcium phosphate carbonate-polyglycolide has been synthesized using
precipitation method. Calcium phosphate carbonate was resulted by pouring CaCl2.2H2O into
NaHCO3 and Na2HPO4.2H2O solutions using precipitation method at temperature of 70oC
and N2 atmosphere to eliminate foreign ions. Porous polyglycolide was resulted from solid
state polymerization of sodium chloroacetate at temperature of 212oC. The composite was
synthesized by adding polyglycolide into NaHCO3 and Na2HPO4.2H2O using precipitation
method. The precipitate was dried at 110oC for 10 hours after which the precipitate mass was
then measured. AAS analysis presented Ca/P ratio of calcium phosphate carbonate ranged
from 1.46 to 1.67. The presence of polyglycolide was shown by FTIR spectra. The formation
of the composite was indicated by sample mass which was close to the calculation mass. FTIR
spectra of the composite showed the presence of absorption bands of calcium phosphate
carbonate and several groups of polyglycolide.
Keywords : Composite, precipitation, calcium phosphate, polyglycolide
Introduction
Bone is a natural composite material
containing about 55% inorganic mineral, 30%
organic matrix and 15% water [1]. The mineral
component of bone is a form of calcium phosphate
known as hydroxyapatite (HAp). The matrix
component is comprised primarily of Type I
collagen that is highly aligned, yielding a very
anisotropic structure. This organic component of
bone is predominantly responsible for its tensile
strength and made an important role in skeletal
system to provide the supporting structure for the
body. Bone can remodel and adapt itself to the
applied mechanical environment [2,3]. An accident
or bone disease may cause bone damage that
becomes necessary to replace or recontour the
damage in the healing process. Many materials
have been proposed as useful replacements.
There are several techniques dealing with
bone reconstruction such as allograft, autograft, and
xenograft. Autograft is a bone reconstruction using
one of body parts and implanted to other part from
the same individual. Allograft is implantation from
different individuals in the same species. Xenograft
is implantation from different species. In many
cases, implementation of autograft usually does not
cause refusal response from the host body, but the
availability is limited, moreover this can cause
additional operation and prolongation of operation
time, increased loss of blood, and postoperative
Proceeding Book
pain [4-6]. On the other hand, allograft and

xenograft sometimes cause refusal response from
host and the availability is also limited. These may
also
become media for contagious diseases.
Synthetical biomaterials are expected to be able to
overcome those problems. Good biomaterial for
bone implantation must be biocompatible,
bioactive, no corrotion, non toxic, has long time
stability, strength, and easy to obtain.
Hydroxyapatite has been widely used as a
bone replacement material in restorative dental and
orthopaedic implant as its chemical and
crystallographic structure being similar to that of
bone mineral. Bone substitution needs composite of
biomaterial within polymer and ceramics
biomaterial. One type of polymer matching with
this problem is Polyglycolide (PGA). Polyglycolide
(or polyglycolic acid) is a well-known biomaterial
with
excellent
biocompatibility
and
biodegradability lead to its widespread application
in medicine as material for bone implants and bone
fixation device. The existence of polymer as matrix
is not forever in the body, after apatite mineral
coalesces in bone and forms healthy bone, the
polymer matrix will disappear. It means that
polymer must be accepted in biological
environment and biodegradable [7].
This research aimed to synthesize calcium
phosphate carbonate-polyglicolide composite by
precipitating calcium, phosphate, and carbonate
compound on polyglycolide.
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January 24, 2009
ISBN : 978 979 19201 0 0
concentrations to make this mixture was shown in

Table 1.
Precipitation processes were controlled at
a temperature of 70oC and N2 atmosphere. N2
atmosphere was purposed to eliminate foreign ions
from background. To control homogeneity of
solution,
stirring
was
performed
during
precipitation using magnetic stirrer. Calcium
phosphate carbonate solution as the result of the
precipitation was decanted for about 12 hours
before filtering. Afterward, the precipitate was
dried using furnace at 110oC for 10 hours. Mass of
precipitate was then measured using analytical
balance. This measurement aimed to compare the
mass of calcium phosphate carbonate mineral, the
mass of PGA matrix and the mass of mineralmatrix composite.
Experimental
Polymer matrix preparation
Sodium chloroacetate was placed in a
ceramic cup and heated using furnace with heating
rate of 0.2oC/minute until polymerization
temperature, 212oC, was reached, in nitrogen
ambience, resulting polyglycolide (PGA) and NaCl.
The next step was washing processes by solving
polyglycolide powder into hot water and stirred for
about 4 minutes. Then the polyglycolide was
filtered and dried at 110oC for one hour.
Precipitation of calcium phosphate carbonate
Solution of calcium phosphate carbonate
was prepared from NaHCO3 and Na2HPO4.2H2O
mixed inside a beaker glass. CaCl2.2H2O was then
poured into the solution. Variation of
Table 1 Concentration variation of calcium phosphate carbonate

Sample
code
CaCl2.
2H2O
NaHCO3
Na2HPO4.2H2O
(50ml)
(50ml)
(50ml)
A
0.2
0.2
0.2
0.334
0.2
0.2
Precipitation of calcium phosphate carbonatepolyglycolide composite

The calcium phosphate carbonatepolyglycolide composite was synthesized in the
same way as calcium phosphate carbonate. Prior to
the precipitation of composite, polyglycolide was
added into NaHCO3 and Na2HPO4.2H2O solutions.
Characterization
AAS analysis was used for identifying
concentrations of Ca, Na dan P in samples. FTIR
analysis used to determine contain of complex
bench in composite.
Results and Discussions

Polymer matrix preparation
Porous polyglycolide was obtained
through polymerization of sodium chloroacetate at
212
C resulting polyglycolide and sodium
chloride (as by product). According to the analysis
of DSC (Figure 1), sodium chloroacetate used in
this study polymerized at 212 C. This point was
different from previous study eventhough the type
of sodium chloroacetate was identical (MERCK,
98%) [7]. Therefore, it is suggested for further
study that it is important to analyze the
polymerization point of sodium chloroacetate.
Figure 1 DSC analysis of sodium chloroacetate.
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January 24, 2009
ISBN : 978 979 19201 0 0
The pore of polyglycolide was obtained through

the elimination of sodium chloride through out the
immersion of polyglycolide into aquadest. It was
assumed that the washing treatment succeeded in
eliminating the sodium chloride in the
polyglycolide as there was a decrease in mass of
polyglycolide as high as 50 % wt (Table 2). This
assumption was proven through FTIR spectra.

There was no peak that indicates the presence of
sodium chloroacetate. Although there was C=O
band, it did not belong to sodium chloroacetate.
XRD spectra of this obtained polyglycolide also
showed that there was only polyglycolide peak.
Table 2 Mass of polyglycolide before and after washing process by warm aquadest
Mass (grams)
Before
After
Mass lost
(%)
5.0012
2.4092
51.83
4.9049
2.1817
55.52
Polyglycolide
band of polyglycolide tended to disturb the 3 of

phosphate band so that this band appeared as if
there was a shoulder at around 1210 cm-1. While the
appearance of (COO, CH) band of polyglycolide
tended to fades the 3 of carbonate band. At higher
concentration, polyglycolide tended to generate the
formation of type A carbonate apatite that occurs at
900 cm-1.
The formation of composite

The preliminary indicator of the composite
formation was given by the measured mass which
was close to the calculated mass. Table 3 shows
the measured and calculated mass of the composite.
Another indicator was given by the presence of
absorption bands of both calcium phosphate
carbonate and several groups of polyglycolide in
the FTIR spectra as presented in Table 4.
The addition of polyglycolide forming the
composite gave an influence to the FTIR spectra,
particularly at stretching asymmetric vibration ( 3)
of phosphate band (around 1025 cm-1) and
stretching asymmetric vibration ( 3) of carbonate
band (around 873 cm-1). The occurrence of (C-O)
Table 3 Mass of samples

Sample
code
A1
A2
A3
B1
B2
B3
Mass mineral
from
precipitation
mineral
matrix
water
Mass
PGA
55%
60%
70%
55%
60%
70%
30%
30%
20%
30%
30%
20%
15%
10%
10%
15%
10%
10%
0.7263 g
0.6658 g
0.3806 g
0.8918 g
0.8175 g
0.4671 g
1.3316 g
1.6350 g
Calcium phosphate carbonate is indicated

by the appearance of (CO32-) and
(PO43-). In
samples without polyglycolide, the FTIR spectra of
those samples are similar. There is no significance
effect in Ca/P ratio.
However, when polyglycolide as a matrix
was present, sample A has a distinct difference
from sample B. Sample A1 has lower transmittance
of all bench compared to sample B1 and so did
sample A2 and B2. However, as the percentage of
Proceeding Book
Mass
composite
formed
1.8414 g
1.7406 g
1.5585 g
2.1915 g
2.1613 g
1.8901 g
Mass
calculation
percentage
(%)
2.0579 g
1.9974 g
1.7122 g
2.5268 g
2.4525 g
2.1021 g
89.48
87.14
91.02
86.73
88.12
89.91
matrix in the composite decreased, the effect of

Ca/P is almost undetected as there was no
significant difference in percentage of transmission
between sample A3 and B3. For all samples, it was
also observed that composite of sample A (A1, A2,
and A3) has lower Ca/P ratio compared to
composite of sample B (B1, B2, and B3) as
presented by Tables 5 and 6 showing the
concentrations and ratio of Ca and P in samples.
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Table 4 Calcium phosphate carbonate and polyglycolide absorption band in samples

Code of
samples
A
A1
A2
ACA*
900.594
900.594
A3
B
B1
B2
B3
900.594
900.594
Calsium phosphate carbonate wavenumber (cm-1)

CO32- (v3)
PO43- (v1)
PO43- (v3)
CO32- (v2)
873.596
1467.65
962.305
1025.94
873.596
1043.30
873.596
1025.94
873.596
873.596
873.596
873.596
873.596
1467.56
958.448
1060.66
1060.66
1095.37
1060.66
1035.59
PO43- (v4)
568.898
568.898
565.898,
607.467
561.184
603.610
603.610
568.098
568.898
Polyglycolide wavenumber (cm-1)

Code of
samples
(C-H)
(C=O)
in ester
(COO, C-H)
A1
A2
A3
B1
B2
B3
2962.13
2958.27
2962.13
2962.13
2958.27
2958.27
1751.05
1751.05
1747.19
1747.19
1747.19
1751.05
1417.42
1417.42
1417.42
1419.35
1417.42
1419.35
Sample code
A
A1
A2
A3
B
B1
B2
B3
Proceeding Book
Ca
28.70
18.83
15.96
22.20
Concentration (%)
Na
3.36
2.01
2.13
2.82
25.88
1.49
19.85
1.47
18.89
1.33
21.06
1.45
Table 5 Concentrations of Ca, Na, andP
815.742
806.742
806.099
815.742
815.742
815.742
P
14.32
9.96
8.02
11.48
12.94
9.13
9.41
10.10
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ISBN : 978 979 19201 0 0
Table 6 Ratio of Ca/P

Sample code
Ca/P
1.55
A1
1.46
A2
1.54
A3
1.49
1.55
B1
1.67
B2
1.55
B3
1.61
Conclusion
Polyglycolide and sodium chloride were
resulted from the polymerization of sodium
chloroacetate at 212 C. Porous polyglycolide
obtained from elimination of sodium chloride
through the immersion of polyglycolide into
aquadest could be used as a matrix of calcium
phosphate carbonate. Precipitation method enabled
the synthesis of composite of calcium phosphate
carbonate-polyglycolide.
The appearance of
polyglycolide indicated by the disturbance of both
3 phosphate and carbonate bands. Phosphate band
tended to have a shoulder occurrence at its 3,
while carbonate band tended to fade away.
References
[1].
[2]
Aoki, H. 1991. Science and medical

applications of Hydroxyapatite. Institute for
Medical and Dental Engineering. Tokyo
Medical and Dental University.
Mickiewicz, RA. 2001. Polymer-calcium
phosphate composites for use as an
Proceeding Book
[3]
[4]
[5]
[6]
[7]
injectable
bone substitute.
Department of Materials Science and
Engineering, Massachusetts Institute of
Technology.
Emily Y. Ho. 2005. Engineering Bioactive
Polymers for the Next Generation of Bone
Repair. Drexel University.
Dewi, SU. 2007. Analisis Kuantitatif,
Kekerasan dan Pengaruh Termal Pada
Mineral
Tulang
Manusia.
Fakultas
Matematika dan Ilmu Pengetahuan Alam,
Institut Pertanian Bogor.
Langenati, R, Ngatijo, Widjaksana, Latief,
A,
Sugeng,
B.
2003.
Aplikasi
Hidroksiapatit
Di
Bidang
Medis.
Tangerang: Batan, Puspitek Serpong.
Epple, M and Herzberg, O.1997. Porous
Polyglycolide . J Biomed Mater Res (Appl
Biomater) 43: 8388.
Schwarz, K and Epple, M. 1998.
Biomimetic Crystallization of Apatite in a
Porous Polymer Matrix. Hamburg: Institute
of Inorganic and Applied Chemistry,
University of Hamburg.
544

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ISBN : 978 979 19201 0 0
An In-Situ Neutron Diffraction Study of -Bi2Mo2O9 and -Bi2MoO6 as

Partial Oxidation Catalysts
Hamzah Fansui1 and Dong-ke Zhang2
1

Institut Teknologi Sepuluh Nopember,
Kampus ITS Sukolilo, Surabaya, Indonesia, 60111.
2
Centre for Petroleum, Fuels and Energy
The University of Western Australia,
35 Stirling Highway, Crawley, Perth, Western Australia 6009
Abstract
The dynamics of lattice oxygen in -Bi2Mo2O9 and -Bi2MoO6 as catalysts for partial oxidation of
propylene to acrolein was investigated using the neutron diffraction technique. The catalyst
characterization experiments were carried out under reaction conditions at 300, 350 and 400 oC using
the Medium Resolution Powder Diffraction (MRPD). The unit cell of the -Bi2Mo2O9 was seen to
expand isotropically to the (111) face with increasing temperature, indicating that there was no
important atomic coordinate changes in the temperature range studied. On the other hand, the unit
cell of the -Bi2MoO6 expanded to the (110) face. The difference suggests that the two catalysts have
different activation mechanisms in catalysing the partial oxidation reaction. Structure refinement of
both catalysts under the in-situ conditions shows that certain lattice oxygen ions are more mobile than
others. The Oxygen ions No. 3 and 18 in -Bi2Mo2O9 and No. 1 and 5 in -Bi2MoO6 are the mobile
oxygen ions in the lattice. The mobile lattice oxygen ions are the most probable active oxygen for the
selective oxidation of propylene to acrolein
Keywords: Acrolein, Bismuth molybdate, In-Situ Neutron Diffraction, Partial Oxidation,
Propylene.Write five keywords
Introduction
Bismuth molybdates have long been known as active
catalysts for selective oxidation of olefins. There are
several phases of bismuth molybdates but only three
of them are known to be active for partial oxidation of
propylene to acrolein, namely , and bismuth
molybdates.
Many researchers believe that lattice oxygen
in bismuth molybdate catalysts plays an important
role in determining the activities of bismuth
molybdates in catalysing the partial oxidation of
olefin. It has been proven that the oxidation reaction
uses the lattice oxygen and follows the Mars-van
Krevelen mechanisms [1-2]. Several studies have also
shown that the lattice oxygen ions are involved in the
oxidation process [1, 3-6]. Furthermore, Haber [7]
mentioned that the ease of oxygen movement in
bismuth molybdates, by the formation of shear plane
and rearrangement of corner-linked metal oxides into
edge-linked octahedrals of molybdenum as well as
tungstate oxide, favour their activities and selectivity
towards acrolein formation.

Experimental
Proceeding Book
The catalysts used in the present study were

prepared using the co-precipitation method from
Bi(NO3)3.5H2O and (NH4)6Mo7O24.4H2O solutions.
Molar ratio of Bismuth to Molybdenum was 1 and 2
for the preparation of -Bi2Mo2O9 and -Bi2MoO6,
respectively. The suspension was kept in a water bath
at 70oC and stirred well to evaporate the liquid
slowly until it became a paste. The paste was then
dried at 120oC for 20 hrs in air. The dried cake was
crushed and calcined in air at 250o for 2 hrs followed
by calcination at 650oC for 24 hrs for -Bi2Mo2O9
and at 480oC for 20 hrs for -Bi2MoO6. Room
temperature structure of the catalysts thus prepared
was characterized using both X-ray and Neutron
diffraction techniques. XRD analysis employed Cu
K radiation operated at 40 kV and 30 mA. Neutron
diffraction analysis was carried out using the High
Resolution Powder Diffraction (HRPD). A
monochromatic neutron beam at a wavelength of
1.495 was applied. In-situ neutron diffraction
analyses were carried out using the Medium
Resolution Powder Diffractometer (MRPD) with a
monochromatic neutron beam at a wavelength of
1.665 . The catalyst characterisation was carried out
at 300, 350 and 400oC in air and in a simulated
reaction atmosphere comprised of 1% C3H6, 2% O2
and 97% He in a special quartz cell reactor [8]
545

January 24, 2009
ISBN : 978 979 19201 0 0
(Figure 1). All diffractograms were used to refine the

lattice parameters, inter-atomic distances and thermal
parameters, using the LHPM Rietica refinement
method [9].
a=5.482(0), b=16.199(1), c=5.509(0),

=90.0
=90.0 =90.0 and unit cell volume V=489.2 as
reported by Teller et al. [11]. Structure refinement
results of the beta and gamma phases from their room
temperature HRPD and XRD using their
corresponding structural model give slightly different
unit cell parameters as shown in Table 1.
(a
Figure 1. A schematic of the special sample

cell for the in-situ MRPD analyses

Figure 2 shows HRPD diffractograms and
refinement fit of room temperature -Bi2Mo2O9 and
-Bi2MoO6. Search and Match results using Jade 6.0
and PDF (Powder Data File) database version 2
reveals that the bismuth molybdate catalysts prepared
in this experiment are -Bi2Mo2O9 and -Bi2MoO6.
The beta phase corresponds to ICSD
(b)
(Inorganic Crystal Structure Database) collection No.
201742 based on structural model reported by Chen
Figure 2. Graphical representation of the
and Sleight [10]. The unit cell in the model is
refinement results of room temperature
monoclinic with unit cell parameters a=11.972(3),
HRPD diffractograms. (A) -Bi2Mo2O9
b=10.813(4), c=11.899(2),
=90.0
=90.1(0)
and (B) -Bi2MoO6.
=90.0 and unit cell volume V=1540.4. Meanwhile,
the gamma phase corresponds to ICSD collection No.
47139 where the unit cell is orthorhombic and
Table 1.
Refined unit cell parameters of bismuth molybdates of room temperature X-ray and Neutron
(HRPD) diffractograms.
Parameters
-Bi2Mo2O9
X-ray
-Bi2MoO6
Neutron
X-ray
Neutron
Volume ( )
1534.05(9)
1538.27(5)
489.41(3)
490.84(2)
a ()
11.954(0)
11.965(0)
5.484(0)
5.489(0)
b ()
10.799(0)
10.810 (0)
16.209(0)
16.225(0)
c ()
11.883(0)
11.893 (0)
5.506(0)
5.511(0)
( o)
90.000
90.000
90.000
90.000
(o)
90.143(3)
90.139(2)
90.000
90.000
90.000
90.000
90.000
90.000
The dynamic changes on the structure of

beta and gamma phases under reaction condition
Proceeding Book
(increasing temperature and reaction atmosphere)

were studied by HRPD. The unit cell of the -
546

January 24, 2009
ISBN : 978 979 19201 0 0
Bi2Mo2O9 expanded isotropically as the temperature

increased (Figure 2.a). The isotropic unit cell
expansion revealed that there is no important atomic
coordinate change in the temperature range studied.
The thermal parameters did not increase as the
temperature increased. However, some oxygen ions
(No. 3 and 18) in the lattice had larger thermal
parameters than the others. These oxygen atoms were
laid in the cavities of the -Bi2Mo2O9 crystal and
bonded to molybdenum and bismuth ions. On the
other hand, the unit cell of the -Bi2MoO6 expanded
more in the a and c directions than in the b direction
(Figure 2.b). Some oxygen ions in the lattice (No. 1
and 5) experienced greater increases in their thermal
parameters than the others. Oxygen No 1 was
0.80%
situated between the Mo-O and Bi(2)-O layers while

Oxygen No 5 was on the Mo-O layer and closer to
the Bi(1) layer than the other oxygen ions in the MoO layer. The specific thermal parameters of Oxygen
ions No 1 and 5 indicate that they are probably the
key in controlling the catalyst activity for the
selective partial oxidation. In addition, the less lattice
expansion in the b direction suggests that oxygen
atoms bridging the layers were strongly bonded to
molybdenum and/or bismuth, except Oxygen No 1.
The lattice oxygen atoms with high thermal
parameters at high temperatures are the source of the
oxidising oxygen responsible for the selective
oxidation of propylene to acrolein.
2.50%
1.00%
0.70%
2.00%
0.80%
2.00%
1.50%
0.40%
0.30%
0.20%
0.10%
0.00%
275
1.00%
a
b
c
beta
Cell Volume
300
0.50%
a, b and c
0.50%
0.70%
0.60%
1.50%
0.50%
a
b
c
Cell Volume
0.40%
0.30%
1.00%
0.20%
Cell Volume
0.60%
Cell Volume
a, b, c, and beta
2.50%
0.90%
0.50%
0.10%
325
350
375
Temperature (oC)
(a)
400
0.00%
425
0.00%
0.00%
275
300
325
350
375
o
400
425
Temperature ( C)
(b)
Figure 2. Percentage of unit cell extensions of a) -Bi2Mo2O9 and b) -Bi2MoO6

4. Y.-H. Han, W. Ueda, Y. Moro-Oka, Applied
Catalysis A: General 176 (1999)
Conclusion
5. L. D. Krenzke, The Kinetics and Mechanism
of Propylene Oxidation over BismuthThe in-situ neutron diffraction study revealed
Molybdate,
that the most probable active lattice oxygen ions
Bismuth(1)Molybdenum(1)Oxygen(12),
responsible for the partial oxidation of propylene
Bismuth(3)Iron(1)Molybdenum(2)Oxygen(12)
to acrolein are oxygen No 3 and 18 in -Bi2Mo2O9
and Uranium(1)Antimony(3)Oxygen(10), in
and No. 1 and 5 in -Bi2MoO6. The active oxygen
Chemistry. 1977, The University of
atoms in both bismuth molybdates are slightly
Wisconsin: Milwaukee, USA. p. 163-175.
different in their nature. In the
phase, active
6.
E.
Ruckenstein, D. B. Dadyburjor, The
oxygen ions are laying in the crystals cavity and
Journal
of Physical Chemistry 84 (1980) 26
directly bonded to molybdenum and bismuth ions,
7.
J.
Haber,
in R. K. Grasselli, J. F. Brazdil (Ed.),
while in the
phase, the active oxygen are
Catalysis
by Transition Metal Oxides,
sandwiched between molybdenum and bismuth
American
Chemical
Society, Washington, D.
oxide layers.
C., 1985, p. 1-19
8. H. Fansuri, Catalytic Partial Oxidation of
References
Propylene to Acrolein: The Catalyst Structure,
Reaction Mechanisms and Kinetics, Ph.D
1. J. M. Thomas, W. J. Thomas, Principles and
Thesis, Curtin University of Technology, 2005,
Practice of Heterogeneous Catalysis, VCH
p. 49
Verlagsgesellschaft mbH, Weinheim, 1997
9. C. J. Howard, B. A. Hunter, LHPM Manual, A
2. A. Bielanski, J. Haber, Oxygen in Catalysis,
Computer Program for Rietveld Analysis of
Marcel Dekker, Inc., New York, 1991, p. 472X-ray and Neutron Powder Diffraction
479.
Patterns, Australian Institute of Nuclear
3. M. M. Bettahar, G. Constentin, L. Savary, J.
Science and Engineering, Sydney, 1997.
C. Lavalley, Applied Catalysis A: General 145
10. Chen, H-Y & Sleight, AW, 1986, 'Crystal
(1996)
Structure of Bi2Mo2O9: A Selective Oxidation
Catalyst', Journal of Solid State Chemistry, vol. 63, pp. 70-75.
Proceeding Book
547

January 24, 2009
ISBN : 978 979 19201 0 0
11. Teller, RG, Brazdil, JF & Grasselli, RK, 1984,

'The Structure of
-Bismuth Molybdate,
Bi2MoO6, by Powder Neutron Diffraction',
Acta Crystallographica C, vol. 40, pp. 20012005.
Proceeding Book
548

January 24, 2009
ISBN : 978 979 19201 0 0
A Neutron Diffraction Study of Co and Mn Incorporation into

AlPO4-5 Lattice
Hamzah Fansuri1, Mei Dong2, Sawsan Jamil Freij3, Jianguo Wang2 and Dong-ke Zhang4
1

Institut Teknologi Sepuluh Nopember,
Kampus ITS Sukolilo, Surabaya, Indonesia, 60111.
2
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O.
Box 165, Taiyuan, Shanxi 030001, China
3
Centre for Fuels and Energy-Curtin University of Technology, GPO Box U1987, WA 6845, Australia
4
Centre for Petroleum, Fuels and Energy, The University of Western Australia,
35 Stirling Highway, Crawley, Perth, Western Australia 6009
h.fansuri@chem.its.ac.id
Abstract
Incorporation of Co2+ and Mn2+ into the lattice of AlPO4-5 to alter its acidity and redox properties in
order to improve the AlPO catalytic activity was studied using the neutron diffraction and analysed
using the Rietveld refinement method. Several Co2+ and Mn2+ substituted AlPO4-5 samples were
synthesised using a hydrothermal method and then calcined at 550 oC in air before the neutron
diffraction analyses. Electron microscopy images of the AlPOs showed that they were mainly
agglomerates of hexagonal plates and prisms where no clear difference was observed between Co and
Mn substituted AlPO4-5. Rietveld refinement of the neutron diffraction data in the Pcc2 group
showed that the substitution of aluminium with either cobalt or manganese did not affect the structure
of AlPO4-5 significantly and no other phases of Mn or Co were detected. This is an indication that
the Co and Mn ions were homogenously distributed in the AlPO4-5 framework and will have similar
catalytic selectivity to that of unsubstituted AlPO4-5. Further refinements are required to fully
understand the Co2+ and Mn2+ incorporation into the AlPO4-5 lattice.
Keywords: Neutron diffraction, Aluminophosphate molecular sieves, Transition metal
incorporation.
Introduction
Aluminophosphate molecular sieves (AlPOs) are
important materials for their potential applications in
catalysis, adsorption and separation. The AlPO4-5
generally consists of a tetrahedral structure of AlO4
and PO4, which corner-share an oxygen atom to build
a three-dimensional framework with molecule-sized
channels [1]. However, the framework lacks acidic
and redox active sites and thus does not possess
catalytic activity. Incorporation of transition metal
ions can alter the AlPO catalytic activity. For
example, CoAPO-5 is an excellent catalyst for
selective oxidation of alkanes due to its highly
dispersed redox centres and proper pore structure [2].
Although many publications have reported the
synthesis of MeAPOs, little is known about the
detailed nature of the metal incorporation in the
framework. Progress in the designed synthesis of
these microporous catalysts with desired locations of
active sites and well defined atomic environment is
limited due to the lack of adequate knowledge of the
transient active ions from the precursor gel to the
templated solid microporous materials.
Proceeding Book
This paper reports our effort in the

determination of metal incorporation in AlPO4-5
using a neutron diffraction technique. Neutron
diffraction is a sensitive probe for this incorporation
since Al and P have different scattering lengths. The
initial structure model of the Co- and Mn-AlPO4 was
deduced from the unsubstituted AlPOs with a
hexagonal symmetry and strict alternation of Al and P
in the framework (space group P6cc) [3, 4].

Experimental
The Co- and Mn-AlPO4 were synthesised according
to the verified method [5]. Samples were crystallised
at 200 oC for 2, 8, 16 and 24 hours. They were then
calcined in a muffle furnace in air (flow rate: 100
ml/min) with a heating rate of 10 C per minute to 550
o
C and kept at this temperature for 6 hours.
The XRD analyses of all samples were performed
using Cu K radiation operating at 40 kV and 30 mA.
Neutron Diffraction was used to characterise the Co2+
and Mn2+ substituted molecular sieves at room
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ISBN : 978 979 19201 0 0
temperature in air using the Medium Resolution

Powder Diffractometer (MRPD) over 3o 138o of
two-theta. A Ge crystal monochromator was used to
provide a monochromatic neutron beam at 1.665 .
Unit cell parameters were refined using RIETICA, a
rietveld refinement software6. The SEM images were
also taken using a Philips XL30 Scanning Electron
Microscope fitted with a SE, BSE and EDS detectors.

Figures 1 and 2 show diffractograms of NeutronMedium Resolution Powder Diffraction (MRPD) and
XRD, respectively, collected at room temperature for
10
samples
of
cobalt
and
manganese
aluminophosphate. The patterns have shown that the
crystallinity of of Mn-AlPO increases with the
crystallization time while the crystallinity of Co-AlPO
reaches a maximum at 8 hour of crystallization and
decreases with longer crystallization time. The
crystalinity is taken as the ratio between the peak
heights versus FWHM (Full Width of Half
Maximum).
3000
2500
2000
1500
1000
500
0
5
15
25
35
45
55
65
75
85
95
105
115
125
Figure 5 The refined data for Co-AlPO4-5

crystallised for 16 hours
3500
3000
2500
2000
1500
1000
500
0
5
25
45
65
85
105
125
Figure 6 The refined data for Mn-AlPO4-5

crystallised for 16 hours
Figure 1
Diffractograms of Neutron-Medium
Resolution Powder Diffraction (MRPD)
Blue line = CoAlPO4-5 and Red line =
MnAlPO4-5.
The data from diffractograms (MRPD and XRD)

were refined in Pcc2 group using Rietica Software to
investigate the effect of metal substitution on the
crystal structure and parameters. An example of
refinement results is shown in Figures 3 and 4 for the
MRPD data for Co and Mn aluminophosphate,
respectively.
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Analysis of the X-ray diffractogram of Co- and

Mn-AlPO4 reveals that their structure are better
described as having a Pcc2 rather than P6cc
symmetry. Preliminary refinements, either with X-ray
or neutron diffraction patterns, have shown that
substitution of aluminium with either cobalt or
manganese did not affect the bulk structure of AlPO45 significantly and no other phases of Mn or Co were
detected.
It indicates that Co and Mn are
homogenously distributed in the AlPO4-5 framework.
Table 1 compares the crystal lattice parameters for the
unsubstituted
and
metal-substituted
aluminophosphate
samples
studied.
Further
refinements are required to fully understand the
structure by varying the atomic positions with degree
of substitution
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Table 1. Unit cell parameters for pure AlPO4-5 and the metal-substituted AlPO4-5
Phase
a
AlPO(Unsubsituted
)
CoAlPO (2 hrs)
CoAlPO (8 hrs)
CoAlPO (16 hrs)
CoAlPO (24 hrs)
MnAlPO (2 hrs)
MnAlPO (8 hrs)
MnAlPO (16 hrs)
MnAlPO (24 hrs)
13.794
13.770
13.775
13.771
13.771
13.772
13.778
13.778
13.773
Unit cell (Pcc2)

b
8
6
6
5
6
6
6
6
23.901
23.859
23.868
23.876
23.879
23.888
23.882
23.871
23.880
13
10
10
9
11
11
11
11
8.417
8.389
8.392
8.391
8.393
8.396
8.396
8.395
8.394
2
1
1
1
1
1
1
2
.
The possibility that the Co- and Mn-AlPO45 having preferred orientation is justified by their
electron microscope images as shown in Figures 5
and 6.
Electron microscopic images show that the
AlPO4 mainly consists of agglomerates of hexagonal
plates and some prisms. It is also shown that both
Co-AlPO4-5 and Mn-AlPO4-5 have two main
morphologies; each morphology is dominated by
Figure 3
Proceeding Book
different crystallographic faces. This may induce

preferred orientation effect in the diffraction patterns
as some faces would be expressed more than others,
depending on the overall composition of the samples
analysed.
SEM Images of CoAlPO4-5, crystallised for 24 hours
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Figure 4
SEM Images of MnAlPO4-5, crystallised for 24 hours
Conclusion
The present study has shown that crystals of Co
and Mn substituted aluminophosphates consist
mainly of agglomerates of hexagonal plates and
prisms. No clear difference was observed between
Co and Mn substituted AlPO4-5. Preliminary
refinements of the neutron diffraction data in the
Pcc2 group have shown that the substitution of
aluminium with either cobalt or manganese did not
affect the structure of AlPO4-5 significantly and no
other phases of Mn or Co were detected. This is
an indication that Co and Mn are homogenously
distributed in the AlPO4-5 framework and may
suggest similar selectivity to that of the
unsubsituted AlPO4-5.
References
1.
2.
3.
4.
5.
6.
Ribeiro, F.R., F. Alvarez, C. Henriques, F.

Lemos, J.M. Lopes, and M.F. Ribeiro, J. Mol.
Catal. A, 96 (1995) 245.
G. Sanker, R. Raja, J. M. Thomas, Catal. Lett.,
55 (1998) 15.
Bennet JM, Cohen JP, Flanigen EM, Pluth JJ,
Smith JV, Am Chem Soc Symp Ser 218
(1983)109.
Qiu S, Pang W, Kessler H, Guth JL, Zeolites 8
(1989) 440.
Harry Robson (Editor), Syntheses of Zeolitic
Materials, Elsevier B.V., Amsterdam, 2001.
p.90.
C. J. Howard, B. A. Hunter, LHPM Manual, A
Computer Program for Rietveld Analysis of
X-ray and Neutron Powder Diffraction
Patterns, Australian Institute of Nuclear
Science and Engineering, Sydney, 1997
Proceeding Book
552

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Relation Between Addition of Alumino-Silicate with Alkali-Silica Reaction and

Geopolimer Product
Anggaria Maharani, Lukman Atmaja1 and Hamzah Fansuri
Laboratories of Physical Chemistry, Department of Chemistry, Faculty of Mathematic and Natural Sciences, Sepuluh
Nopember Institut of Technology (ITS), Surabaya, Indonesia.
1)
email: lukman_at@chem.its.ac.id,
Abstract
Geopolymers have been studied for several decades due to their excellent mechanical and thermal properties,
as well as chemical and fire resistance. Geopolymer were synthesized via reaction of aluminosilicate
material, fly ash, with alkalinesilicate solution at ambient temperature. In this paper, geopolymers was
modified by the addition the amount of insoluble additive, -Al2O3 (Corundum) and SiO2 (Quartz) to Si/Al
variation. The result show that the geopolymer product (Si/Al=5.0) has highest strength (65 MPa) as compare
to other sample. The current work used XRD, the quartz and mullite were found both of fly ash and
geopolymer product. This study also indicates that not only amorphous phases but also crystalline phases
involve in the geopolymerization process.
Keywords : crystalline phase reactivity in geopolymerization, fly ash utilization, geopolymers, alkali-silica
reaction
Introduction
Power stations, using coal like-fuels, are
worldwide energy source, including Indonesia will
dramatically increase its coal fired-power station to
produce 10000 MW electricity. The generation of
electricity by coal combustion produces fly ash (8090%) and bottom ash (10-20%) [1,2]. It is considered
that volume of fly ash production will reach 800
MTon in around the world) in 2010 where only a
small part (20-30%) of these ashes are used at present
[3]. Thus, the increase of coal fired power station will
give serious problems to particularly our environment
like air pollution, contaminant of water and decrease
of ecosystem quality.
The important advances in the search for
new application for fly ashes are being achieved.
Among the main achievements is a new inorganic
material which is called geopolymer. Geopolymer is a
synthetic material analogues of natural zeolite.
Geopolymer materials has excellent mechanical
properties, including fire and acid resistance [4].
These properties make geopolymer an alternative
construction material compared to Portland cement.
Geopolymer has better strength than Portland cement
[5].
Fly ashes contain sufficient amount of
alumina and silica that can be used as source
Proceeding Book
materials for geopolymerisation reaction. It was

reported that the type and nature of the starting
materials will directly affect the final physical and
chemical properties of a geopolymer [6]. Moreover,
the main mineral component in fly ash like quartz and
mullite might also affect the geopolymer product due
to their activation reaction [7]. Geopolymer from Fly
ash with more amorphous phases are more reactive
than those contains more crystalline phases [8]. Xu
and van Deveneter also reported that Si and Al in
amorphous phase are more dissolvable in an alkaline
solution than the crystalline phase [9].
The aim of the present study is to prove the
role of Si and Al in crystalline phases and their
contribution to Si/Al ratio in the geopolymerisation
process and product. The present study explores the
effect of the insoluble silicone and aluminium content
in a series of composition on the mechanical strength,
microstructural and to identify and quantify such
products.
Experimental
Materials
Fly ash class F (according to ASTM C 61803) used in the synthesis of all geopolymer matrices
was obtained from Asam-asam power station in South
Kalimantan, Indonesia. Its chemical composition is
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shown in Table 1. The composition of fly ash was

determined by X-ray fluorescence (XRF) method.
Quartz/SiO2 (Merck, 99%), Corrundum/-Al2O3
(Merck, 95%), sodium silicate, distilled water and
analytical-grade NaOH were used throughout all
experiment.
Geopolymerisation
The ash and either quartz or corundum in the
required proportions were mixed with the activating
solution to prepare cylindrical specimens (15x30
mm). Alkaline solution (NaOH, sodium silicate and
H2O) and source materials were mixed for 3 minutes.
The mixture was cast in plastic moulds and vibrated
for 10 second. Specimens was cured at 60C for 24h.
At the end of the curing process, the specimens were
removed from the oven and kept in the mould for 7,
14, 21 and 28 days.
Compressive strength testing was carried out

on the molded, cylindrical speciments with 1:2
diameter to length ratio. Three cylinders of each
sample were tested and the experimental values being
averaged. All samples were tested at 7, 14, 21 and 28
days. An Torsee Universal Testing Machine Au-5
20490 was used for all tests.
Morphology, FT-infrared analysis and X-ray
diffraction
The samples were studied by SEM/EDX
using a JEOL JSM-6360LA scanning microscope
equipped with an energy dispersive X-ray at the
accelerating voltage of 10 kV. FT-infrared spectra
were recorded on a spectrometer using the KBr pellet
technique. X-ray powder diffraction data were
obtained using a Phillips PW 1800 diffractometer
with Cu K radiation (40 kV, 30 mA) with scanning
rate 2/min from 5 to 70.
Compressive strength testing

Table 1 Elemental composition Fly ash, expressed as oxides (%)

Mechanical strength
Fig. 1 shows the variation in compressive
strength with curing time for the various working
system (3 cube per test were tested). At short curing
time (7 day), an increase in the soluble silica content
at Si/Al = 5.0 favored the development of high
Proceeding Book
mechanical strength in material (compressive strength

> 50 MPa). At slightly longer curing times (14 day),
however, a substantial increase was observed in the
strength of systems. Longer curing times had a
consistently beneficial effect on the mechanical
strength of the all matrices.
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70
Compressive strength (MPa)
65
7d
14 d
21 d
28 d
60
55
50
45
40
35
30
25
20
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
The mol ratio of Si/Al
Fig. 1. Mechanical strength vs mol ratio of Si/Al for various curing time
The geopolymerisation of fly ash, fly ash-corundum,

and fly ash-quartz was conducted with the mol ratio
of Si/Al was varied from 1.5 to 6.0 in NaOH and
Na2SiO3 solutions. It was found that all geopolymer
products have satisfactory compressive strength
(Fig.1). When a mixture of fly ash and corundum was
geopolymerised, theere was no significant change in
the compressive strength, namely around 34 MPa. On
the other hand, addition of SiO2 (Quartz) results in
dramatic increase in the compressive strength. It was
faound that the strength reached up to 65 MPa,
doubled than those prepared by corrundum addition.
The Figure also shows that the increase in Si/Al ratio
improve the compressive strength of geopolymers.
However, when the ratio is higher that 5 it start to
declines.
The variation in mechanical strength as a
result of variation in Si/Al ratio has a relation with
material reactivity. The propety can be analysed by
elemental analysis using ICP for silicone and
aluminium dissolved from the material in a strong
Proceeding Book
alkaline solution. The analysis results showed that the

solubility of aluminium in corundum was only
0.067% while in fly ash it was 4.57%. The same trend
was also shown by quartz where the solubility of
silicone was only 2.06%. Thus, it can be seen that a
high reactivity raw materials were needed to produce
a high performance geopolymer.
3.2
Sample
crystallinity
and
FT-Infrared
Characteristics
X-ray powder diffraction pattern for the
material studied, including original fly ash, SiO2 and
corundum, are shown in Fig. 2. In contrast to the
other two, the fly ash shows a substantial amorphous
phase (hump registered between 2 = 20 and 2 =
30) in its structure with the peaks of the quartz
(SiO2, JCPDS 03-0444) and mullite (3Al2O3.2SiO2,
JCPDS 15-0776) as a remainder. It has been reported
[9] that source materials like fly ash are usually have
a higher reactivity in geopolymerization process.
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Fly ash
Quartz
Corundum
10
15
20
25
30
35
40
45
50
55
60
65
70
Fig. 2. The XRD pattern of fly ash, quartz and corundum

Fig. 3 shows the XRD pattern of the
geopolymer synthesized at Si/Al molar ratio =3.0;
3.5 and 5.0. The Figure shows crystalline phases
detected in the product of geopolymer, namely quartz
R
R
Q
Si/Al=5.0 + TiO2
M
Q
R M
MM
Q/M Q
RQ
M
RR
R
Q R
M
Si/Al=3.5 + TiO2
Si/Al=1.5 + TiO2
10
15
20
25
30
35
40
45
50
55
60
65
70
Fig. 3. The XRD pattern of some geopolymer

products. Q= quartz, M= mullite, and R= Rutile
and mullite. The addition of insoluble material

(Quartz and Corundum) increased the intensity of
quartz (in 2 = 27, increase from 438 to 487) and
mullite (in 2 = 42, increase from 89 to 291).
The FTIR spectra of the original fly ash and
geopolymer products are shown in Fig. 4. The fly ash
spectrum shows one broad absorbance registered at
1089cm-1 which is ascribed to T-O asymmetric
stretching vibration (T=Si or Al). Absorbance at
466cm-1 ascribed to 4 (O-Si-O) bending modes of
SiO4 tetrahedra and around 782 cm-1 is assigned as
symmetrical stretching of Si-O-Si [6,10]. An
absorbance at 679 cm-1 is assigned for quartz as a
part of the fly ash component[11]. There was no
significant differences between the FTIR pattern of
fly ash and the geopolymer products which means
that the most vibrant forms of the molecular chains
existing in the raw materials are retained in the
geopolymer
product
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Si/Al = 6.0
Si/Al = 5.0
1427
1081
784
1018
690
560
Si/Al = 3.5
459
Si/Al = 3.0
Si/Al = 1.5
1464
782
1089
679
466
Fly ash
Wave number (cm-1)

Fig. 4. FTIR spectra of fly ash and geopolymers product
On the other hand, the geopolymer products either

with or without insoluble material additives were
found to have vitreous phases comprising of SiO2 and
Al2O3 namely quartz and mullite. The presence of
quartz in the FTIR spectra is shown by a series of
bands located at around 1081, 784 (double band), 690
and 460 cm-1. Meanwhile, the presence of mullite is
shown by bands at around at 560 cm-1 (band
associated with the octahedral aluminium present in
mullite) [12]. Absorption band which is appeared at
around 1427 cm-1 has been assigned to the presence
of the sodium bicarbonate [10] as a result of the
reaction between excess sodium with atmospheric
carbondioxide. The geopolymer absorption band at
around 1089 cm-1 (asymmetric stretching vibration of
Proceeding Book
T-O) is shifted to between 1081 and 1018 cm-1. The

shift indicates that the vitreous components in fly ash
are reacted with the alkali activator and the alkaline
aluminosilicate gels are being formed [11].
Microscopic morphology
The micrographs presented in this paper
depict the typical microstructure by the material at
Si/Al ratio (Fig. 5 and 6). Fig. 5 is a SEM image
showing the characteristic morphology of the original
fly ash, quartz and corundum. The ash (a) consists of
a series of spherical vitreous particles of different
sizes (diameter ranging from 0.2 to 5 m). While
quartz powder (b) shows a prismatic shape with
particle size mostly larger than 50 m and corundum
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powder displays hexagonal shapes with particle size
mostly smaller than 5 m.
(a)
(b)
(c)
Fig. 5. SEM Picture (a) original fly ash, (b) Quartz, (c) Corundum
Fig. 6a shows the geopolymer product
without insoluble material additives. The picture
correspond to a geopolymer cured for 28 days. Fly
ash particles which have reacted with the alkali
solution are observed to co-exist with some unreacted
sphere (see
). Fig. 6b shows the geopolymer
product with corundum addition. Corundum crystals
(see ) are detected under the matrix layer on the
broken surface. Fig. 6c shows the product with quartz
additive. Almost all quartz particles reacted with the
alkali solution.
Proceeding Book
The
main
reaction
product
from
geopolymerization in alkaline condition is sodiumalumino-silicate gel that are getting compacted during
precipitation step with more gel proceeding from
other particles giving place to a geopolymer matrix.
The EDX analyses for the geopolymer matrix show
that the Si/Al ratio in the main reaction products is
3.5 in the geopolymer with no additive), 3.0 with 0.03
mol corundum additive and 5.0 with 0.3 mol quartz
additive. This phenomenon suggests that some added
corrundum and quartz may still exist in the
geopolymer product.
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(a)
(b)
(c)
Fig. 6. SEM images of Geopolymer product
(a) Si/Al=3.5, (b) Si/Al=3.0 and (c) Si/Al=5
Conclusion
Product of geopolymers from fly ash and
insoluble material (Quartz and corundum) has been
successfully synthesized. It is found that there is an
interrelationship among the insoluble additives that
affect the final structure and properties of geopolymer
products. It was shown that the reactivity of starting
material affect the mechanical properties where
highly reactive starting material produces high
mechanical strength. The lower reactivity of the
quartz, the interaction between the source material
and the alkaline solution and the reinforcing effect
caused by the unreacted quartz particles give
satisfactory mechanical strength of the formed
geopolymers. The Si/Al ratio (5.0) gives the highest
mechanical strength. This study also indicates that not
Proceeding Book
only amorphous phases but also crystalline phases

involve in the geopolymerization process.
Acknowledgements
The authors gratefully acknowledge funding
from the Directorate General of Higher Education,
Indonesia, under Hibah Pasca grant.
References
[1]
[2]
Bankowski, P., Zou, L., Hodges, R.,Using

inorganic polymer to reduce leach rates of
metals from brown coal fly ash, Mineral
Engineering, 17 (2004) 159-166.
Perera, D. S., Uchida, O., Vance, E.R.,
Finnie, K.S., (2007), Influence of Curing
Schedule on the Integrity og Geopolymers,
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ISBN : 978 979 19201 0 0
[3]
Journal of Material Science, 42 (2007)

3099-3106.
Bakharev, T.,
Thermal Behaviour of
Geopolymers Prepared using Class F Fly
Ash and Elevated Temperature Curing,
Cement and Concrete Research, 36 (2006)
1134-1147.
[8]
[9]
[4]
[5]
[6]
[7]
Fletcher, A.R., MacKenzie, K. J. D.,

Nicholson, L. C., Shimida, Shiro, The
composition range of aluminoslicate
geopolymers, Journal of European
Ceramic Society, 25 (2005) 1471-1477.
Fernandez-Jimenez, A., Palomo, A., and
Criado, M., Microstructure Development
of Alkali-Activated Fly Ash Cement : A
Descriptive Model, Cement and Concrete
Research, 35 (2005) 1204-1209.
Van Jaarsveld, J.G.S., van Deventer, J.S.J.
and G.C. Lukey., The Effect of
Composition and Temperature on The
Properties of Fly Ash- and Kaolinite-Based
Geopolymers,
Chemical
Engineering
Journal, 8 (2002) 63-73.
Xu, Hua, Lukey, G. C., van Deventer, J. S.
J., (2006), The effect of Ca on Activation of
Proceeding Book
[10]
[11]
[12]
Class C-, Class F-Fly ash and Blast Furnace

Slag, Cement and Concrete Research, xx
(2006) xxx-xxx.
Xu, Hua, Van Deventer, J.S.J., The
geopolymerisation
of
aluminosilicate
minerals, International Journal of Mineral
Processing, 59 (2000) 247-266.
Xu, Hua dan J.S.J., Van Deventer,
Geopolymerisation of Multiple Minerals,
Journal of Mineral Engeneering, 15 (2002)
1131-1139.
Lee, W. K. W., J.S.J., Van Deventer, The
effect of the inorganic salt contamination on
the strength and durability of geopolymers,
Colloidal and Surface A : Physicochem.
Eng. Aspects., 211 (2002) 115-126.
Fernandez-Jimenez, A., Palomo, A.,
Composition and Microstructure of lcali
Activated Fly Ash Binder : Effect the
Activator, Cement and Concrete Research,
35 (2005) 1984-1992.
Criado, M., Fernndez-Jimnez, A., Palomo,
A., (2007), Alkali activation of fly ash :
Effect of the SiO2/Na2O ratio Part I : FTIR
study, Microporous and Mesoporous
Materials, 106 (2007) 180-191.
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Dye Sensitized Solar Cell Building by Anchored-Tio2

Wahyuningsih,1,2 Joshua Watts3, Indriana Kartini,2 Narsito2, Lianzhou Wang3, Max Lu3
1
Department of Chemistry, Faculty Mathematic and Natural Science Sebelas Maret University
Ir. Sutami Street, 36A, Kentingan, Surakarta, Indonesia.
E-mail: w.sayekti.yahoo.com, phone: 62-274-368381
2
Department of Chemistry, Faculty Mathematic and Natural Science Gadjah Mada University
Sekip Utara, Yogyakarta 55281, Indonesia
3
ARC Centre of Excellence for Functional Nanomaterials, Level 5 AIBN Building 74 Brisbane Qld 4072
Australia
Abstract
In this study, mesoporous TiO2 with 30 nm pore size diameter synthesized using the template method
with a short-range ordered-framework structure was successfully used as an electrode material in
dye-sensitized solar cells. The higher light-to-electricity energy conversion efficiency is attributed to
the novel physicochemical properties of mesoporous TiO2, which include high surface area, anchored
by silyl agent, and uniform nanochannels. The high surface area adsorbs large quantities of the
sensitized dye, resulting in the generation of a higher photocurrent density. A significant influence of
the mesopore structure on photovoltaic performance was also observed based on these novel
properties. The photovoltaic performance of the dye-sensitized solar cells composed of mesoporous
TiO2 is expected to be further improved through the use of an anchor group, which has higher thermal
stability. Therefore, mesoporous TiO2, used as an electrode material in DSSCs, may provide a means
of obtaining higher efficiencies in dye sensitized solar cells, possibly approaching their theoretical
efficiency value in future.
Keywords: belum ada
Introduction
Since the powering work of Regan and Gratzel (1), a
great attention has been paid to dye sensitized solar
cell (DSSC) as cheap, effective and environmentally
benign candidates for a new generation of solar
power. Solar cells based on dye-sensitization of TiO2
electrodes are regarded as a regenerative low-cost
alternative to conventional solid-state devices. DSSC
is a photoelectrochemical device which effectively
utilizes a property of nanocrystaline wide bandgap
metal oxide semiconductor porous electrode.
Nanocrystalline TiO2, particularly in the anatase
phase, has been extensively investigated as a potential
material for dye-sensitized solar cells (DSSCs) (1).
Currently, this kind of solar cell reaches an efficiency
exceeding 10% offering a realistic option for
converting light to electrical energy. However, it is
not easy to gain 10% efficiency, which is still far
from the theoretical efficiency of 33%.
Generally, a DSSC consists of indium tin oxide,
(ITO), dye modified TiO2 electrode, electrolyte, and a
counter electrode. To establish high energy
conversion efficiency, mesoporous TiO2 electrode of
a large surface area have been investigated
extensively as a key material for DSSC (1). The
efficiency of 10% was obtained by using mesoporous
TiO2 as electrode materials (12). Over the whole
range of 040 mm, the amount of dye adsorbed by the
mesoporous TiO2 films was about 1.52 times greater
Proceeding Book
than that by the P-25 films (12). This high efficiency

is attributable to the physicochemical properties of
mesoporous TiO2, such as surface area, ordered
structure, particles size and uniform pore size (12). In
this study, mesoporous TiO2 was synthesized with
triblock copolymer Pluronic P123 as the structure
direction template to satisfy this need. In order to
make breakthroughs in progress, a great deal of
attention has also been focused on developing new
sensitizers (2,3), new electrolytes (4,8,16,17), new
model counter electrodes (5,10,15) and new
semiconductor electrode materials (2,6,9). Recently,
an efficiency of 10.2% was obtained using a N719
dye as a sensitizer (7), and a new record efficiency of
11.04% was achieved using a modified electrolyte
(11). One of the strategies to improve conversion
efficiency is to increase high harvesting efficiency by
increasing the amount of dye in the TiO2 electrode
using anchoring group onto TiO2 surface.
In this article, we present the photophysic and
photoelectrochemical characteristics of mesoporous
TiO2, anchored by silyl agent, abbreviated as
anchored-TiO2. Photosensitizer was anchored onto
TiO2 surface via anchor group to gain chemical
bonding between TiO2 and dye. Compared to
nanowires or nanorods, mesoporous anchored-TiO2
has a high surface area (approx. 140.1 m2 g-1 after
calcinated at 400oC), and also uniform nanochannels
that can be easily accessed by the electrolyte for I3ion transport. Sensitized anchoring-TiO2 was applied
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January 24, 2009
ISBN : 978 979 19201 0 0
for the electrode of DSSC. The incident photon to

current conversion efficiency (IPCE) of the cell made
from anchored TiO2 was investigated. There are many
factors limiting the cell performance, among which
light harvesting efficiency is the most important.

Materials
Nanocrystaline TiO2 was synthesized via self
assembly-solgel technique adopted followed
previous work (19). Titanium tetra isopropoxide
(TTIP) was purchased from Aldrich, triblock
copolymer
HO(CH2CH2O)20(CH2CH(CH3)O)70
(Mav
=
5750,
designated
(CH2CH2O)20H
EO20PO70EO20; Pluronic P123) was received as a gift
from BASF, acetylacetonate (acac) was purchased
from Merck, 2-propanol (iPr) and hydrochloric acid
(HCl) 37% was purchased from Merck. TiO2 film
prepared on indium tin oxide (resistivity: 10 /cm2)
conductive glass (Asahi Glass, Japan) and Pt coated
FTO conducting glass (Dyesol). Complexes
compound were prepared using CoCl2 from Merck,
aminopropyltrimethoxysilane (APTS) from Aldrich,
and 4-(2-piridilazoresorcinol) (PAR) from Aldrich.
Methanol used as solution of in situ complexes
sensitizer formation was purchased from Merck.
Sealant spacer, aluminum back cover, electrolyte (ELHSE) and N719 dye were purchased from Dyesol.
Instrumental
Crystal structure of TiO2 powders were
analyzed by X-ray diffraction (XRD) measurements
using Cu K radiation (Shimadzu XRD-6000).
Differential thermal analysis (DTA) and thermal
gravimetric analysis (TGA) and fourier transform
infra red spectrophotometer (FTIR) were used to
observe template replacing process. Pore size
distribution and surface area were calculated using N2
adsorption-desorption data from Autosorp NOVA
1000. Scanning Electron Microscope (SEM)
including Energy Dispersive X Ray Analysis (EDX)
specimen (Joel JSM 6360LA) was employed to
investigate the morphology of the anchored TiO2 film.
The absorption and reflectant spectrum was analyzed
by UV-Vis spectrophotometer (SHIMADZU UV
1799 Pharma-Spec) equipped with specularreflectance accessories. Annealing process of TiO2
film preparation was carried out using a Furnace
Carbolite CWF 1300 with a heating rate of 5oC/min
at 400oC for 2 hour.
Preparation of Anchored-TiO2 Photoelectrodes
TiO2 film was fabricated on the indium tin

oxide (ITO) covered glass substrate (Asahi Glass
Japan, 10 /cm2) by doctor bland technique. Anatase
TiO2 particles (7-8 nm in size) were prepared by
using a published method (19). TiO2 pastes were
prepared by adding water, acetylacetonate, and tritonX 100 (10:1:2 v/v). The film thickness was prepared
by SEM. The apparent film size was 5 mm x 5 mm.
The films were annealed at 400oC for 2 hour with a
rising rate of 5oC/min. TiO2 film was immersed in the
anchoring ligand aminopropyltrimethoxysilane (5%)
for 5 times, and then rinsed with methanol creating
anchored-TiO2. Anchored-TiO2 film was immersed in
the Co2+ solution (10-4 M), then in the 4-(2piridylazo) resorcinol (10-4 M) for 2 hour. After dye
adsorption via in situ complexes formation, the colour
of the thin films changed to a deep red.
Solar cell assembly
Stepwise of DSSC building including (1)
preparation of dye sensitised photoanode cell, (2) the
use of Pt-coated on conductive glass electrode, and
(3) assembly of sandwiched dye sensitized solar cell.
The dye-sensitized TiO2 electrode was
incorporated into a thin-layer, sandwiched solar cell
(Fig.8). The area of the TiO2 electrodes was 0.5 x 0.5
cm2. The Pt sputtered on a transparent conducting
glass (SnO2-F) (Dyesol) was used as the counter
electrode. A thermoplastic sealant film spacer (50 m
nominal thickness, TPS 109129-50 from Dyesol) was
used to prevent the cell from short-circuiting when
the counter- and working electrodes were clamped
together. The electrolyte (EL-HSE electrolyte from
Dyesol) was placed inside counter and working
electrodes through a small hole in counter electrode.
Electrolyte addition was kept in vacuum desiccators.
After electrolyte addition (without air bubble
formation), the cell was pressed together with
electrolyte sealer (thermoplastic backed aluminium
strip) in the back side. DSSC cell was tested with a
solar simulator, which has an input power of 250 watt
and able to reach a voltage range of about 0.2-0.5 V.
This indicates that the cell is ready for IPCE
measurement.
Fig 1. Building component of dye sensitized solar cell
IPCE measurement
Action spectra of the monochromatic
incident photon to current conversion efficiency
Proceeding Book
562

January 24, 2009
ISBN : 978 979 19201 0 0
(IPCE) for the solar cells were measured with a Oriel

QE/IPCE measurenment kit Model QE-PV-SI from
Newport Corporation. We employed an AM1.5 solar
simulator with 300 watt Xenon Lamp as the light
source. The incident light intensity was calibrated
with a standard solar cell for silicon solar cell
produced by Japan Quality Assurance Organization
A monochromatic incident photon to current

conversion efficiency (%IPCE) of 0.9 was obtained
at 655 nm composed of mesoporous TiO2. The
photocurrent yield measured at 655 nm was found to
depend on the counter ion of the iodine/triiodine
redox electrolyte.
0.9
0.8
0.8
0.6
IPCE (%)
IPCE%
0.7
0.5
0.4
0.3
0.6
0.4
0.2
0.2
0.1
0
350
0
350
450
550
650
750
850
950
1050
450
550
Wevelength (nm)
650
750
850
950
1050
10
9
8
7
6
5
4
3
2
1
0
IPCE(%)
IPCE(%)
Wavelength (nm)
0.2
0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
750
850
950
1050
Wavelength (nm)
350
450
550
650
750
850
950 1050
Wavelength (nm)
Fig. 2. Incident photon to electron conversion efficiency (IPCE) of (a) mesoporous TiO2/aminosilyl-CoIIpiridylazoresorcinol and (b) P25 TiO2/aminosilyl-CoII-piridylazo resorcinol (c) mesoporous TiO2/N719.
Insert: row photocurrent action spectra along visible region.
Based on the figures, there are correlations
TiO2 based DSSC compared to mesoporous
TiO2/N719 is due to inefficient blocking layer as a
between IPCE spectra (Fig. 10) and UV VIS
consequence
of
the
recombination
of
absorption spectra of related cell (Fig. 11).
photogeneration electrons and holes. The sluggish
Excitation dyes electrons seen in UV VIS
efficient interfacial charge transfer between the
absorption will be injected to the conduction band
TiO2 and dye complexes anchored to the TiO2
of electrode TiO2. The cell performance improves
significantly if the dye acts not only as an absorber
surface also propose the lower result of anchoredbut also as an efficiency blocking layer (SchmithTiO2 based DSSC. Unfortunately, for the second
periods transition metals CoII used in this study, the
Mende et al, 2005). The recombination of
ratio of injection over recapture ratio kinj/kb lower
photogeneration electrons and hole in the band of
that 103.
all solar cells are the main reasons for their less
The nanocrystaline films with particles size
efficiency. DSSCs, in which the electrons and hole
commensurate or smaller that their Bohr radius
exist in separate chemical phases, are subject
exhibits quantum size properties, which can be
almost exclusively to interfacial recombination. We
illustrated in photocurrent action spectra of
suggest the lower result of aminosilyl anchored-
Proceeding Book
563

January 24, 2009
ISBN : 978 979 19201 0 0
mesoporous
TiO2/aminosilyl-CoIIpiridylazoresorcinol (Fig. 2a) and of mesoporous
TiO2/N719 (Fig 2c).. This means that there is a
potential barrier between the particles and that the
particles constituting the film can, in some respect,
be regarded as individual entities. Quantum size
effect occur if crystal size of TiO2 less than 10 nm.
Fig.3 shows dependency of crystal size on
annealing temperature. Annealing until 400OC still
get quantum size TiO2. In the absent of quantum
size effect, the extinction spectrum is described by
the Mies Theory (26). By Mies Theory, a very
small colloidal semiconductor particle removes
light from the incident beam both by scattering and
absorption.
25
should set centered alignment, and the resolution of

scanned picture has to be not less then 300 dpi.
(a)
Crystal Size (nm)
20
15
10
0
0
200
400
600
800
1000
Tem perature (C)
Fig. 3. Dependency of TiO2 crystal size on

annealing temperature. Annealing
temperature rate 5oC/min. ( ____anatase, --rutile)
The BET surface area of mesoporous TiO2
(140.1 m2 g-1) is higher than that of P-25 (approx.
55 m2 g-1), resulting in more dye being adsorbed
per unit thickness of film. The high-adsorption
property of mesoporous TiO2 allows high
photocurrent action spectra properties of DSSC
based mesoporous TiO2 (Fig. 2a and Fig. 2b). The
higher efficiency is attributable to the
physicochemical properties of mesoporous TiO2,
such as high surface area, ordered structure, particle
size and uniform pore size. The results of the
characterization of the mesoporous TiO2 are
depicted in Fig. 4 (data calculations were shown in
Table 1). The pore size distribution was very
narrow and the highest pore diameter was estimated
to be 30 nm. The isotherm is of type IV,
characteristic of mesoporous materials. The
hysteresis loop exhibited by the specimen is mainly
between the H1- and H2-types.The character of
small size distribution explains the low efficiency
in the P25 film, because of the diffusion of I3- ion in
electrolyte become a slow and limits the current
production.
Experiment results can be illustrated in the form of
figures (graphics or picture, see example Figure 1).
Title of figure (10 pts) is set under the figure.
Figure can be formatted single or double column. It
Proceeding Book
(b)
Fig 4. Characteristic of (a) isotherm adsorptiondesorption N2 and (b) pore size distribution
of mesoporous TiO2 (synthesized at molar
=
ratio
of
TTIP/P123/acac/H2O/iPr
1/0,051/0,53/12/30)
Table 1. The BET data and pore characteristic of
TiO2 used in DSSCs cells
Pore
Average
Surface
volume
pore size
area
cm3/g
(nm)
(m2/g)
mesoporous
140.1
216.6
6.2
TiO2
TiO2 P25
58
0.291
1.04
Many researchers have tried to reproduce the
overall efficiency of 10% for N719 DSSC, reported
in 1993 (13). However, this record remained
unmatched for several years until 2001, when a
black dye-adsorbed DSSC gave an efficiency of
10.4 % (14). Sensitization of mesoporous TiO2
using N719 dyes can increase photocurrent action
spectra
compared
with
mesoporous
TiO2//aminosilyl-CoII-pyridilazoresorcinol (Fig 2c).
This report proves that anchoring of carboxylic
group more favour than silyl group, except of metal
ion and ligand influence. Further explanation need
observation of two dyes with the equivalent metal
ions and ligand.
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January 24, 2009
ISBN : 978 979 19201 0 0
The photovoltaic performance of DSSCs

depends largely on the film thickness (12). Wei et.
al. (12) have showed Jsc of the cells composed of
mesoporous TiO2 and P-25 initially increased with
film thickness but then fell off with further
increases in thickness. The film thickness
approximately 20 m for the mesoporous TiO2 film
and that for the P-25 film is fixing with sealant used
as spacer between working electrode and counter
electrode.
On the other hand, the electron
recombination between the electrons injected from
the excited dye to the conduction band of electrode
TiO2 and the I3- ions in the electrolyte becomes
more serious in the thicker films. It should be
pointed out that this IPCE tendency of the cells
made of P-25 less than those of mesoporous TiO2,
indicating that the electron recombination between
the transported electrons and I3- ions in the P-25
film is more serious than that in the mesoporous
TiO2 film (Fig 2). This may contribute to the
differences in electrode material morphology. As
mentioned above, the particle size of P-25 is
approximately 20 nm, while mesoporous TiO2 has a
short-range ordered-framework structure and a
smaller particle size (approx. 78 nm, calculated by
Scherrer equation from Fig. 8), and thus contains a
large number of grain boundaries of homogeneous
nanocrystalline TiO2 along the framework (Fig.5).
Nakade et al.(18,19) report that the diffusion
coefficients of electrons increased with TiO2
particle size. The increasing diffusion coefficients
of electrons were related to the decreased film
surface area and the condition of the grain
boundaries. On the other hand, they also found that
the electron lifetimes decreased with increasing
TiO2 particle size. Therefore, an electrode film
composed of mesoporous TiO2 is conductive to
decreased diffusion coefficients of electrons and
increased electron lifetimes.
Fig. 5. SEM picture of mesoporus TiO2 synthesized

by Pluronic P123 templated at molar ratio of
=
TTIP/P123/acac/H2O/IPr
1/0,051/0,53/12/30
(a)
magnitification
50.000x (b) magnitification 95.000x, and
SEM picture of TiO2 P25 at (a)
Proceeding Book
magnitification 50.000x (d) magnitification

90.000x
Fig.6. SEM photograph of cross

section of
The
ITO/meso
ITO/mesoporousTiO2.
porous TiO2 film was calcinated at 400oC
for 2 hour.
Fig 6. Illustration of mesoporous TiO2 in 30 nm

average pore diameter size with numerous
uniform
aminosilyl
nanochannels.
Aminosilyl nanochannels absorb monolayer
dyes
Our experimental results suggest that the
mesoporous structure plays a key role and is
responsible for the improvement in the performance
parameters. Compared with P-25 nanoparticles,
mesoporous TiO2 has numerous uniform aminosilyl
nanochannels 30 nm in average pore size (Fig 6).
Assuming that the adsorbed dye forms a monolayer
on the inner surfaces of the aminosilyl
nanochannels, and the molecular size of PAR as
organic ligand is approximately 1.20 nm - 2.4
(24), big space is left for electrolyte diffusion. If the
adsorbed dye molecules were stuck in the inner
surface of the channels as a bilayer or aggregated in
the entrances of the nanochannels, the space for
electrolyte diffusion will not further reduced. Under
these conditions, it only need short time for the
electrolyte solution to penetrate and fill all the
nanochannels. Using a little dye of Co2+ complexes
the aggregated adsorption dye molecules in the
entrances of the nanochannels can not hampers dye
adsorption on the inner surface of the
nanochannels. Based on the assumptions mentioned
above, part of the inner surface is be covered by
dye molecules and the electrode film can be used
efficiently. However, over time, the rearrangement
of adsorbed dye might occur accompanied with the
565

January 24, 2009
ISBN : 978 979 19201 0 0
400
350
M i c r o v o l t E n d o u p (m i c r o v o l t)
diffusion of electrolyte solution. On the other hand,

due to anchoring group addition cooperated in TiO2
surface as well as in Co2+-pyridilazoresorcinol
complexes, removing dye together within
electrolyte can be reduced. But aminosilyl
nanochannels with high concentration may increase
cell resistivity due to silyl condensation.
The XRD pattern of mesoporous TiO2
synthesized by self assembly-sol gel method
adopted followed previous work (19) was shown in
Fig. 7. It can be seen that the phase of mesoporous
TiO2 annealed at 400oC show well-crystallized both
anatase (90%) and rutile (10%) peak. The average
crystal size of TiO2 calculated using the Scherer
equation is about 7 nm.
300
250
200
150
100
50
0
0
100
200
300
400
500
600
700
800
Temperature (C)
100
W e ig h t % (% )
80
Fig. 7. X-ray diffraction pattern of TiO2 thin film

on indium tin oxide glass. Synthesized at
molar ratio of P123/acac/HCl/H2O/iPr =
0.05:0.53:1.25:12.00:30.00.
Clean up of template occur at 400oC, due to
organic group burning at that temperature. These
phenomena show at infra red spectras (Fig. 9),
differential thermal analysis (Fig. 10a.) and
thermograph metric analysis (Fig.10b.).
Fig 9. Infra red spectra of TiO2 annealed at (a) 150oC, (b)

300oC, and (c) 400oC.
Proceeding Book
60
40
20
0
0
200
400
600
800
Temperature (C)
Fig.10. Thermal analysis of TiO2 xerogel (a)

differential thermal analysis, and (b)
thermographymetric analysis
We report here a novel dyes, cobalt-based
photosensitizer, was prepared via in situ complexes
formation. The UV Vis spectra of Co2+, Co2+-APTS
complexes, and Co2+-APTS-PAR complexes in
methanol show in Fig. 11. It exposed that visible
absorption of Co2+-APTS-PAR complexes is very
far above the ground due to chromophore ligand of
4-(2-piridylazo)resorcinol. The specular absorption
spectra of the TiO2 sample show in Fig. 11a. The
band gap of the anatase crystal as calculated for the
absorption edge in the visible region was found to
be 3.02 eV, respectively. This result is appropriate
with Eg value of TiO2 anatase and rutile literatures
about 2.99 3.32 eV (20, 21, 22). Addition of
anchoring ligand of APTS, and Co2+ complexes can
move absorption spectra at visible region slightly
(Fig 12c).
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January 24, 2009
ISBN : 978 979 19201 0 0
Fig 11. UV VIS spectras of (a) Co2+ ion in

methanol solution, (b) Co2+-APTS
complexes solution in methanol, and (c)
Co2+-APTS-PAR complexes in methanol
TiO2 as an electrode material. This high efficiency

can be attributed to the novel physicochemical
properties of mesoporous TiO2, which include high
surface area, uniform nanochannels and a
homogeneous nanocrystalline TiO2 several nm in
size arranged along the framework. The high
surface area anchored-TiO2 allows adsorption of a
large volume of dye, resulting in a higher incident
photon to current efficiency. The photovoltaic
performance of the dye-sensitized solar cells
composed of mesoporous TiO2 is expected to be
further improved through the use anchor group,
which has higher thermal stability. Therefore,
mesoporous TiO2, used as an electrode material in
DSSCs, may provide a means of obtaining higher
efficiencies in dye sensitized solar cells, possibly
approaching their theoretical efficiency value in
future.
Acknowledgements
This work was supported by Minister of
Education of Indonesia under Sandwich Program
2008 visiting in ARC Centre of Excellence for
Functional Nanomaterials, Australian Institute for
Bioengineering and Nanotechnology, University of
Queensland.
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Fig 12. UV VIS spectras of (a) TiO2 film onto ITO
glass, (b) aminosilane-TiO2 film onto
ITO glass, and (c) aminosilane-TiO2/dye
film onto ITO glass
High absorption spectra at ultraviolet region,
shown in Fig. 12, exhibits one pyridyl based -*
transition (245 nm) and one metal-to-ligand charge
transfer (MLCT) bands at 550 nm superimposed
with weakly d-d transition. Like those of bipyridyl
complexes of ruthenium(II), their intense visible
absorptions are due to excitation into initially
singlet metal-to-ligand charge transfer (1MLCT)
states via t2g * electronic transitions. However,
cobalts weaker ligand field places the metalcentered antibonding eg orbitals lower in energy
than the ligand * orbitals. As a consequence,
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state is populated via intersystem crossing and
persists for nano - to microseconds, cobalt
complexes crossover to a ligand field (LF) state.
There is a concurrent and substantial loss of excited
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An improvement photocurrent action spectrum
was achieved by applying anchored-mesoporous
Proceeding Book
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S. Nakade, T.Kanzaki, W.Kubo, T.Kitamura,
Y.Wada, S.Yanagida, 2005, Role of
electrolytes on charge recombination in dyesensitized TiO2 solar cell (1): the case of solar
cell using the I-/I3- redox couple, J. Phys Chem
B Condens Matter Mater surf Interface
Biophys., 109(8), 3480-3487.
S. Yanagida, S. Nakade, Y. Saito, W. Kubo, T.
Kitamura, and Y. Wada, Charge transport and
optimization for dye-sensitized nano-porous
TiO2 solar cells, Material and Life Science,
Graduate School of Engineering, Osaka
University Suita, Osaka 565-0871, Japan.
Yun, H., Miyazawa, K., Honma, I., Zhou, H.,
Kuwabara,
M.,
2003,
Syntesis
of
Semicrystallized Mesoporous TiO2 Thin Fims
using
Triblock
Copolymer
Templates,
Materials Science and Enginering C, 23, 487494.
Li, Y., Hagen, J., Schaffrath, W., Otsckik, P.,
Haaner, D., 1999, Titanium dioxide Films for
Photovoltaic Cells Derived from a Sol gel
Process, Solar Energy and Solar Cells, 56,
167-174.
Castillo, N., Olgun, D., Conde-Gallardo, A.,
2004, Structural and morphological properties
of TiO2 thin films prepared by spray pyrolysis,
REVISTA MEXICANA DE FISICA, 50 (4),
382387.
Janczarek, M., Kisch, H., Hupka, J., 2007,
Photoelectrochemical
characterization
of
nitrogen-modified TiO2, Physicochemical
Problems of Mineral Processing, 41, 159-166.
J.T. Hupp and Y.Dong, 1994, Intervalence
energy effect accompanying double crown
encapsulation of the Creutz-Taube ion; an
interpretation based on three site mixing,
Inorg. Chem., 33 4421-4424.
H. Groenzin, O.C. Mullins, Petroleum
asphaltene molecular size and structure,
Schlumberger-Doll Research, 728-732
A. Hagfeldt, M. Gratzel, 1995, Ligh-induced
redox reactions in nanocrystalline systems,
Chem. Rev., 95, 49-68.
L. Schmidt-Mende, J. E. Kroeze, J.R. Durrant,
Md. K. Nazeeruddin, M. Gratzel, 2005, Effect
of hydrocarbon chain length of amphiphilic
ruthenium dyes on solid-state dye sensitized
photovoltaic, NANO LETTER, 5, 7, 13151320.
568

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Synthesis and Characterization Of PVA/Montmorillonite

Khoirul Himmi Setiawan1, Is Fatimah2
1
Research and Development Unit for Biomaterials LIPI, Bogor, Indonesia,

Email: khoirul_himmi@yahoo.com
2
Chemistry Dept., Islamic University of Indonesia, Yogyakarta, Indonesia,
Email: isfatimah@fmipa.uii.ac.id
Abstract
Polyvinyl alcohol (PVA)/montmorillonite composites were prepared by intercalation in solution
system. Their physicochemical properties as the function of PVA to montmorillonite mass ratio were
investigated with X-ray diffraction (XRD), surface area analyzer and Fourier Transform Infra Red. The
results showed that PVA chains could be intercalated into the silica interlayer space of montmorillonite
and the properties are affected by the PVA to montmorillonite mass ratio. Due to FTIR and surface area
analyzer data, it can be concluded that there are no significant surface properties of
PVA/montmorillonite within the range of 1% to 3% w.t clay content. However, the XRD pattern of
materials show the effect of the mass ratio in that the highest d001 produced at the ratio of 1% PVA in
the PVA/montmorillonite synthesis. These data are the indication of intercalation process to exfoliating
process as the PVA concentration increase controlled by the cation exchange capacity.
Keywords: intercalation, montmorillonite, PVA/Montmorillonite
Introduction
Nanocomposite materials, consisting of inorganic
nanolayers of montmorillonite (MMT) clay and organic
polymers, have evoked intense interest lately because
their unique characteristics have the potential to be used
in many commercial applications. Nanostructured
polymer-inorganic composites, mixed at the molecular
level or near molecular level, are much different from
the conventional composites with incorporation of a
variety of additives in the polymer matrices. In the
polymer-inorganic nanocomposites, strong chemical
bonds or interactions such as van der Waals forces,
hydrogen bonding, or electrostatic forces, often exist
between the polymer and inorganic components (Jung
et al., 2006).
Several useful polymer/clay nanocomposite
materials have been produced. At present, polymer/clay
hybrids are one of the most important classes of
synthetically engineered materials. They can be
transformed into new materials possessing the
advantages of both organic materials, such as light
weight, flexibility, and good moldability, and inorganic
materials, such as high strength, heat stability, and
chemical resistance (Chang et al., 2003). The flexibility
and processability of polymer matrices based on watersoluble polymer such as poly-vinyl alcohol (PVA) with
excellent optical properties and good compatibility with
additives can provide good mechanical properties.
Proceeding Book
Poly-vinyl alcohol (PVA) is a water-soluble

polymer extensively used in paper coating, textile
sizing, and flexible water-soluble packaging films.
These applications stimulate interest in improving the
mechanical, thermal, and permeability properties of thin
nanocomposite films, ultimately with the hope of
retaining the optical clarity of PVA (Strawhecker &
Manias, 2000). PVA nanocomposite materials may
offer a viable alternative for these applications to heat
treatments or conventionally filled PVA materials. The
flexibility and processability of polymer matrices based
on water-soluble polymer such as poly-vinyl alcohol
(PVA) with excellent optical properties and good
compatibility with additives can provide good
mechanical properties. There are several publications
associated with the preparation and properties of
PVA/clay nanocomposites prepared by solution
dispersion technique (Carrado et al.,1996, Wang &
Wu, 1997, Strawhecker & Manias, 2000).
Recently, PVA/clay nanocomposites are found to
display novel properties, which can be observed from
two dissimilar chemical components combining at the
molecular level. Kokabi reported that nanocomposite
hydrogels based on PVA and organically modified
montmorillonite clay were introduced as novel wound
dressings, which prepared by the cyclic freezing
thawing method. PVA/clay nanocomposite hydrogels
showed excellent physical and mechanical properties
which met the essential requirements of ideal wound
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January 24, 2009
ISBN : 978 979 19201 0 0
dressings. Based on swelling measurements, they

exhibited high capability in absorbing fluid, so
recommended for exudative wounds. Because of their
unique mechanical properties, i.e. very high elasticity,
they could be excellent candidates for wounds under
high stresses. The proper values of the water vapor
transmission rates of PVA nanocomposite hydrogels
indicated that they could keep moist environment on
interface of the wound and dressing to accelerate the
healing process (Kokabi, Sirousazar, & Hassan, 2007).
And though many research about poly/clay have
been reported, sinthesis and characterization of
nanocomposite hydrogels based on clay is not yet
studied in Indonesia. With enormous clay resources,
Indonesia need more advanced and sustaine research in
developing poly/clay, leads to some novel
nanocomposites with improved performance properties,
which may be potentially used in wide range application
such as optics and biomedicinal technology. This paper
will focus on review the unique structural properties of
PVA/Montmorillonite (MMT) clays made by
intercalation system. Physiochemical properties of
PVA/MMT will be analyzed by FT-IR, X ray
diffractometer, and Surface Area Analyzer.
80oC for 24 hours. Dry sample resulted was washed

with aquadest. Further, PVA-clay composite are
designated as PVA/MMT 1%, 2% and 3% respectively
and for comparison purpose, montmorillonite clay
encoded by MMT.
Physiochemical characterisation of the samples was
studied including surface area analysis (nitrogen
adsorption at 77 K), X-ray diffraction (XRD), and
Fourier Transform Infra Red (FT-IR) identification. Xray powder diffraction patterns were obtained by using a
Shimadzu X6000 diffractometer, at 40 kV and 30 mA,
and employing Ni filtered Cu K radiation

Material structure of Montmorillonit clay was identified
by X-Ray Diffractmeter to study precursor effect from
PVA
toward
physiochemical
properties
of
Montmorillonit. Figure 1 shows XRD curves of
Montmorillonit and PVA hybrids with different clays at
1, 2 and 3 w.t % clay content. Wide-angle X-ray
diffraction (XRD) measurements were performed at
room temperature on a Shimadzu X6000 X-ray
diffractometer using Ni filtered Cu K radiation. The
scanning rate was 2/min over a range of 2 = 325.
Experimental
The starting clay used for synthesis was natural
montmorillonite supplied by PT. Tunas Inti Makmur
Semarang, Indonesia. The cation exchange capacity of
clay is 68 meq/100 g. Particle sizes of less than 200
mesh were used in synthesis process. Chemicals consist
of H2SO4 and Poly-vinyl alcohol (PVA) was purchased
from E.Merck.
Synthesis of PVA-montmorillonite
The starting material, montmorillonite was dispersed in
water in the concentration of 10 % w.t and then refluxed
with H2SO4 0.01 M for 6 hours in order to purify clay
from impurities. Sample was filtered and neutralized
until the filtrate was free from Cl- and pH=7. Solid was
dried in oven at 130oC followed by grounding to 200
mesh in particle size. PVA intercalating solution was
prepared by diluting PVA solution with deionized water.
Clay
suspension
was
made
by
dispersing
montmorillonite in water with the concentration of 5%
w.t and stirred for 24 h. PVA intercalation was
performed by slow titration of a PVA solution of under
vigorously stirring at room temperature for 24 hours.
PVA concentrations were varied at 1, 2 and 3 w.t % clay
content. After washing by centrifugation and filtration,
the intercalated solids were dried by heating in oven at
Proceeding Book
Figure 1. XRD patterns of (a) Montmorillonit

(MMT) and (b)-(d) PVA/MMT 1%, 2% and
3% respectively
XRD pattern of MMT shows typical peak of
montmorillonite at 2 = 5,9275o (d = 14,898 ) and 2
= 19,915o (d = 4,454 ) with significant intensity. Other
typical peaks such as 2 = 20,18o and 2 = 23,57o,
confirm montmorillonite content. Compared to XRD
pattern of Boyolali clay reported by Simpen et. al.
(2003), the intensity of typical peak from
montmorillonite used in this study shows less
crystalline. Beside of montmorillonite typical peak,
other mineral content such as caolinite showed at 2 =
12,2o (d = 7,24); 2 = 24,86o (d = 3,57 ); and 2 =
19,88o(d = 4,46 ). Generally, XRD pattern showed
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January 24, 2009
ISBN : 978 979 19201 0 0
that clay used in this research classified into

indicating the PVA presence in the interlaminar spaces
montmorillonite mineral.
though not throughout, since if this were the case, the
The main basal spacing (d001) peak reflections of
degree of disorder would be much greater. In other
montmorillonte (MMT) are well defined, indicating a
hand, PVA/MMT 3% w.t shows less d001 than
very ordered structure. Figure 1 shows that intercalation
Montmorillonite (MMT). This is caused by polymer
of PVA into Montmorillonite cause basal spacing
grafting which form agregrat in the interlaminar spaces
displacement to the left along with the increasing of d001
of aluminosilicate structure. The data about interlayer
from PVA/MMT 1% w.t and PVA/MMT 2% w.t. In the
spacings of clay modified by PVA with various
presence of PVA, the peaks for both clays show the
intercalation agent concentration showed on table 1.
characteristics of a moderately disordered material,
Table 1. interlayer spacings of Montmorillonit and PVA/MMT Nanocomposite
SAMPLE
2 (FWHM)
MMT
PVA/MMT 1% (w.t)
PVA/MMT 2% (w.t)
PVA/MMT 3% (w.t)
Figure 2 shows the FT-IR spectrum for MMT,
PVA hybrids with different clays at 1, 2 and 3 w.t %
MMT content It is well known that pure MMT shows
three strong peaks at 455, 520, and 1045 cm1. These
6.30
6.15
6.06
6.70
Basal spacing d001
14.47
14.82
15.04
13.61
peaks are associated with the bending mode of Si-O,
the stretching vibration of Al-O, and the stretching
vibration of Si-O, respectively.
Figure 2. FT-IR spectra of (a) MMT, (b) PVA/MMT 1%, (c) PVA/MMT 2%, (d) PVA/MMT 3%
FT-IR spectrum all of the PVA/MMT
Sample
Active Surface Area (m2/g)
nanocomposite microspheres show the presence of
45,684
MMT
the -OH stretching vibration in the region of 3000188.05
1
PVA/MMT 1% (w.t)
3600 cm after the intercalation process. It indicates
215.72
PVA/MMT 2% (w.t)
that the surfaces of the PVA/MMT nanocomposite
251.77
PVA/MMT 3% (w.t)
microsphere were covered with the hydroxyl groups.
Surface area of Montmorillonite (MMT), PVA
While FT-IR spectrum of PVA/MMT 3% show
hybrids with different clays at 1, 2 and 3 w.t % MMT
significant intensity of alkyl typical peak (CH sp3)
content showed on table 2. It is obvious that specific
on 2800 3000 cm-1, other both PVA/MMT 1% and
surface area increase along with the increase of PVA
2% show no significant peak there.
concentration intercalated. Information about the
influence of PVA concentration toward increasing of
specific surface area cant definitely explaine the
Table 2. Surface area of Montmorillonit and
physiochemical properties of material sinthesized. So,
PVA/MMT
Proceeding Book
571

January 24, 2009
ISBN : 978 979 19201 0 0
it needs more explanation about pore distribution

presented on figure 3.
Strawhecker, K. E., & Manias, E. (2000). Chem

Mater, 12 , 2943.
Figure 3. Pore distribution of PVA/MMT hybrids

material
PVA/MMT 1% show formation of new specific
pore at 32 (mesopore), while PVA/MMT 2% show
no dominant pore formed. Preconception about the
effect of polymer grafting which form agregrat in the
interlaminar spaces of aluminosilicate structure is
confirmed by formation of two kind dominant pore
mode from PVA/MMT 3%, around 32 dan 56. It
can be assumed that there is grafting structure
forming clay layer aggregation which is responsible
to form mesopore.
Conclusion
PVA intercalation into montmorilonite structure
to form PVA/MMT composite shown the effect of
PVA precentage in composite to the physicochemical
characters of materials. From the XRD and surface
area analysis data
it is concluded that the
intercalation with 1% and 2% PVA give the clay
structure intercalation followed by increasing spesific
surface area of materials. These physicochemical
character gained grafting structure by the use PVA of
3% as revealed by XRD, pre distribution analysis and
FTIR analysis.
References
Carrado, K. A., Thiyagarajan, P., & Elder, D. L.
(1996). Clays Clay Miner,44 , 506.
Chang, J. H., Jang, T. G., Ihn, K. J., Lee, W. K., &
Sur, G. S. (2003). Journal of Applied Polymer
Science, 90 , 32083214.
Jung, H. M., Lee, E. M., Ji, B. C., Sohn, S. O., Ghim,
H. D., Cho, H., et al. (2006). Fibers and
Polymers, 7 , 229-234.
Kokabi, M., Sirousazar, M., & Hassan, Z. M. (2007).
European Polymer Journal,43 , 773781.
Proceeding Book
572

January 24, 2009
ISBN : 978 979 19201 0 0
Structure and Characterizations TiO2/TS-1 with Variation of

Calcination Temperature
Maria Ulfa* Didik Prasetyoko
Chemistry Department of Mathematic and Science Faculty
Institut Teknologi Sepuluh Nopember
Surabaya
*
e-mail: mariaulfa8@gmail.com
Abstract
Cathechol and hidroquinon are used in a broad range application from pharmaceuticals,
photography to polimer industries. Cathechol and hidroquinon can be synthesized from
phenol hydroxylation with H2O2 as oxidant and Titanium Silicalite (TS-1) as catalyst. TS-1
has great properties, such as high activity and selectivity to oxidation reaction. However, its
hydrophobic site leads to slow H2O2 adsorption toward the active site of TS-1.
Consequently, the reaction rate of whole reaction is low. Titanium oxide (TiO2) as metal
oxide can give acid site to catalysts. TiO2 has acidic properties, which is depend on
calcination temperature due to phases transformation of anatase-rutile. In this research,
The TiO2 is impregnated into TS-1 then its prepared with variation of calcination
temperature. The novel catalyst, TiO2/TS-1, will be more hydrophilic at certain calcination
temperature compared to TS-1 and rate of the hydroxylation phenol reaction will be faster.
Keywords: TiO2/TS-1, hydroxylation of phenol, calcination temperature
Introduction
Cathechol and hidroquinon are used in a large application
of the modern chemical industry such us pharmaceuticals,
photography to polimer industries (1). TS-1 which was
firest synthesized by Taramasso et al in 1983 has shown
excellent catalytic activity in organic oxidation reactions
using hydrogen peroxide as oxidant under mild conditions.
In organic oxidation reactions such us hydroxylation
phenol, many work have been done to enhance the the
phenol selectivity due to the industrial importance of
hydroxylation of phenol in the synthesis hydroquinone and
cathechol. The ability of TS-1 to catalyze a wide variety of
oxidation transformation including hydroxylation of phenol
with aqueous hydrogen peroxide had led to extensive
research worldwide on the synthesis of related heterogenous
catalyst for liquid phase oxidations (2)
The catalytic activity of TiO2 is strongly

influenced by its structure. TiO2 is usually obtained
by hydrolysis of titanium oxide, followed by
annealing in the presence of oxygen. Porter et al. [3]
studied microstructural changes in commercial
Degussa P-25 TiO2 due to heat-treatment. The
powder was annealed from 600 to 1000 C. With the
increasing calcination temperature the apparent
crystallite size and rutile content in the catalyst
increased, whereas the specific surface area and the
rate of phenol photodecomposition under UV
irradiation decreased. The same effect was observed
by Reddy et al. [4] for catalytic activity obtained by
TiCl4 hydrolysis and calcination at low temperatures,
between 100 and 600 C. A marked increase in the
Proceeding Book
crystallite size and a decrease in lattice strain were

observed for catalysts annealed above 600 C. The
rate of methylene blue degradation in UV increased
with increasing calcination temperature from 400 to
700 C. Calcination above 700 C resulted in a
smaller rate constant, mainly due to partial
transformation of anatase to rutile. The catalytic
activity of the titanium oxide is related mainly to its
acid properties. Some author have reported that the
catalyst contain Lewis acid sites which are
responsible for the activity [10,11,14]. In this study,
TS-1 loaded with titanium oxide has been synthesized
and used as acidic catalysts in which the Ti atoms in
TS-1 acts as oxidative acid sites while titanium oxide
deposited on the surface of TS-1 acts as Lewis acid
sites. The effect of calcinations temperature of
titanium oxide on the the structure and properties of
the catalyst was investigated.

Preparation of sample
TS-1 containing 1% mol of titanium was prepared
according to a procedure describe earlier using
tetraethyl ortosilicates (Merck,98%), tetraethyl
ortotitanat (Merck 98%, TEOT) in 2-propanol,
tetrapropylammonium hydroxide (Merck 20%
TPAOH in water) and distilled water. The gel was
charged into a 150 mL autoclave and heated at 175oC
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January 24, 2009
ISBN : 978 979 19201 0 0
under static condition. The material was recovered

after 4 days by centrifugation and washed with excess
distilled water. A white powder was obtained after
drying in air at 100oC overnight. The solid material
was then calcined in air at 550oC for 4 h.
Sample TS-1 loaded with titanium oxide
(TiO2/TS-1) was prepared by the impregnation
method using tetraethyl ortotitanat TEOT precusor.
TS-1 calcined was dried in oven at 110oC overnight
for 24 h. After that, the necessary amount of titanium
oxide was dissolved in 2-propanol (Merck 98%) to
obtain the desired metal loaidng and the required
quantity of pre-dried of TS-1 was immediately added
to the clear solution with stirring. The mixture was
stirred at room temperature for 3 h. The solid was
recovered by evaporating the 2-propanol at 80oC.
The acid hydrolysis was performed by addtion of 20
mL solution of 0,5 M HNO3 in disttiled water and
aged overnight, followed by heating at 120oC until
dryness. The solid was then washed with distilled
water for three times and finally dried at 110oC for 24
h. The white solid was calcined at 400, 500, 600, and
700oC for 4 h.
Titanium oxide was prepared by hydolysis of
tetraethyl ortotitanat (TEOT) at room temperature.
The white solid was revcovered by filtration, washing
with water and drying at 100oC overnight. Finally,
the solid was calcined at 550oC for 4h.
Characterizations
All sample were characterized by powder X-ray
diffraction(XRD) for crystallinity and phase content
of the solid material, using Bruker Advance D8
difractometer with Cu K Cu K ( = 1.5405 ) as the
diffracted monochromatic beam at 40 kV and 30
mA,. The patern was scanned in the 2 ranges
between 550o at a step 0,02 o and step time 1s.
Infrared (IR) spectra of the samples were collected on
Shimadzu Fourier Transform Infrared (FTIR)n
spectrometer with a spectral resolution of 2 cm1,
scan 10s, at temperature 20 oC with KBr wafer
Samples
TS-1
400 TiO2/TS-1
500 TiO2/TS-1
600 TiO2/TS-1
700 TiO2/TS-1
TiO2
methode. Infrared spectra of the samples were

recorded at room temperature in the hydroxyl region
of 1400-400 cm1.
Hydrophobycity of catalyst was also analisized by
using water adsorption technique. In a typical
experiment, the catalysts were dried in an oven at
110oC for 24 h to remove all the physically adsorbed
water. After dehydration, the sample was exposed to
water vapor at room temperature, folllowed by the
determination of the percentage of adsorbed water as
function of time.

X-ray diffraction
Fig. 1 shows the XRD pattern of XTiO2/TS-1 samples. The
samples are noted as XTiO2/TS-1 where X denoted the
calcination temperature. The diffraction pattern for the
samples with 400, 500, 600 and 700oC of calcination
temperature show similar pattern to that of the parent TS-1
as indicated by the diffraction peaks at 2 = 7,92; 7,94;
8,80; 23,06; 23,08; 23,10; 23,24; 23,26; dan 23,28.
The presenceof all the typical XRD peaks for TS-1
indicates the framework structure has been retained after
calcination. Fig 1 shown that no diffraction lines for
anatase-rutil phases of titanium oxide are observed
indicating that TiO2 is highly dispersed on the surface of
TS-1. It is found that the MFI structure of TS-1 was
maintained after the impregnation titanium oxide and
calcination preparation. However, the XRD peak intensities
of TS-1 decreased when calcination temperature was
increased. This might be due to the decreased in the
precentage amount of TS-1 in the samples as calcination
temperature of TiO2 increased
Table can be illustrated using double (Table 1) or

single (Table 2) column, if necessary. Table started by
table title (10 pts) that set above the table. Table is set
centered alignment, and table limit must not exceed
margin of the page. If the title of the table more than
one row, the second row should be formatted using
hanging indent following the above limit.
Table. 1 The phase dan peak intensities of samples from XRD

Intensities at 2 = 23,06
Phase
Intensities at 2 = 27,52
Cps
( rutile phase)
Cps
2696
MFI
180
2652
MFI
413
2635
MFI
427
2619
MFI
438
2604
MFI
450
0
Rutil
1971
The XRD pattern of TiO2 samples indicated that

structure of TiO2 was rutile. There is no diffraction
line assigned for crystalline phase of titanium
oxide present. This indicated that niobium oxide
was well dispersed on the TS-1. In addition, the
Proceeding Book
peak intensities of TS-1 decreased up to 0,4- 0,9 %

(table 1) as increased calcination temperature. It is
suggested that titanium oxide is either located on
the surface of TS-1 or crystalline phase of TiO2
covering the surface of TS-1 of TS-1.Since of Ti
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January 24, 2009
ISBN : 978 979 19201 0 0
site of TiO2 is larger than size pore entrance of TS1, they should be attached to the external surface of
TS-1. The peak intensities of rutil phase at 2 =
27,52 increased up to 0,77-0,79% (table 2) as
increased calcination temperature. It is suggested
that TiO2 which are dispersed in the surface of TS-1
mainly due to partial transformation of anatase to
rutile
(Ti=O) vibrations[16,17,18,19]. However, this

band can be attributed to the titanium in the
framework, since silicate, a Ti free zeolite, did not
shoe any band at aroud this frequency. In addition,
impregnation and increased temperature calcination
titanium oxide gave rise to no band around 970 cm1
. Therefore, it is concluded that the TS-1 sample
contains Si-O-Ti connections. There is no band
shifting or additional band observed after
impregnation of titanium oxide on TS-1. Ths
finding suggest that both the MFI structure and
titanium framework were still maintained after both
of impregnation and calcination temperature
preparation of titanium oxide.
2, degree
Fig 1. XRD pattern of the samples

Tabel 1. Increased precentage peak intensities of
samples TS-1 and TiO2/TS-1
Persentase
Persentase
pengurangan
pengurangan
intensitas pola
Sampel
intensitas pola
difraksi fase
difraksi TS-1
rutil
(%)
(%)
TS-1
0,036
400 TiO2/TS-1
0,458
0,771
500 TiO2/TS-1
0,635
0,777
600 TiO2/TS-1
0,082
0,783
700 TiO2/TS-1
0,958
0,791
TiO2
-
Fig 2. FTIR Spectra of the samples
Infrared Spectroscopy
The infrared of spectra zeolite lattice vibration
between 1400 and 400 cm-1 are depicted in Fig 2.
According to Flanigen, the absorpstion bands at
around 1100, 800, dan 450 cm-1 are lattice modes
associated with internal linkage in SiO4 or AlO4
tetrahedral and are sensitive to structural changes.
The absorpition bands at around 1230 dan 547 cm-1
are characteristic of the MFI type zeolite structure
and are sensitive to structure changes. All samples
showed a band at around 970 cm-1 . the vibrational
modes at around this frequency may be the result of
several contribution, i.e. the asymmetric streching
modes of Si-O-Ti linkages, terminal Si-O streching
of Si-O-H-(HO)Ti defective sites and tytanyl
Proceeding Book
Fig 3. Hydrophobicity testing before stirring: a. TS1; b. 400 TiO2/TS-1; C, 500 TiO2/TS-1; D.
600 TiO2/TS-1; E. 700 TiO2/TS-1, F.TiO2
a
Fig 4. Hydrophobicity testing before stirring: a.

TS-1; b. 400 TiO2/TS-1; c, 500 TiO2/TS-1;
d. 600 TiO2/TS-1; e. 700 TiO2/TS-1, f.TiO2
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ISBN : 978 979 19201 0 0
As shown in Fig 3 and , it was clearly observed

that the amount of adsorbed water on 700 and 600
TiO2/TS-1 was significantly lower than 400 and
500TiO2/TS-. This might be indicated that
increased calcinations temperature mainly due to
the transformation anatase-rutil phase. The highly
rutil phase of sample at high calcinations
temperature might be due to the agglomeration
titanium oxide (8) in the surface of TS-1.Fig 3 and
4 a, show that TS-1 not well dispersed to aqueous
water. It is indicates that TS-1 have naturally
hydrophobic behavior. Impregnation titanium oxide
to the surface of TS-1 enhanced hidrophylicity
behavior.
Conclusion
Acidid catalyst have been sussesfuly prepared
by the dispersion of titaniumoxide on TS-1 at
modified of calcination temperature increased up to
400 and 700oC. The catalyst have oxidative site due
to titanium located in the framework os silicates,
while octahedral titanium containing hidrophilic
site. The best incresing hidrophilic behavior at 500
TiO2/TS-1 due to highly dispersion of titanium
oxide in the surface of TS-1. Temperature
Calcination at 600-700oC due to decreasing
hydrophilic behavior mainly transformation phase
of anatase-rutil.
Acknowledgements
We gratefully acknowledgement funding from
Directoration General of Highler Education
Indonesiaunder
Hibah
Paska
grant
No
1108/12.7/PM/2008.
References
[1] Almeida, R.M., Noda, L.K., Goncalves, N.S.,
Meneghetti, S.M.P, dan Meneghetti, M.R.,
Transesterification Reaction of Vegetable
Oils, Using Superacid sulfated TiO2-Base
Catalysts, Applied Catalysis A : General ,
Vol. 347, hal. 100105.
[2] Atoguchi, T., Yao, S. (2001), Phenol
Oxidation
over
Titanosilicalite1:Experimental and DFT Study of Solvent,
Journal of Molecular Catalysis A: Chemical,
Vol. 176, hal. 173-178.
[3] Bhattacharyya, A.,Kawi, S.,dan Ray, M.B.
(2004),Photocatalytic
Degradation
of
Orange II by TiO2 Catalysts supported on
Adsorbents, Catalysis Today, Vol. 98, hal.
470-479.
[4] Bonelli, B., Cozzolino, M., Tesser, R., Serio,
M.D., Piumetti, M., dan Garrone, E. (2007),
Study of The surface acidity of TiO2/SiO2
Proceeding Book
Catalyst by Means of FTIR Measurements of

CO and NH3 Adsorption, Journal of
Catalysis, Vol. 246, hal 293-300.
[5] Belessi. V., Lambropoulou, D., Konstantinou,
I., Katsoulidis, A., Pomonis, P., Petridis, D.,
dan Albanis, T. (2007), Stucture and
Photocatalytic Performance of TiO2/Clay
Nanocomposites for The Degradation of
Dimethachlor, Applied Catalysis B :
Enviromental, Vol. 73, hal. 292299.
[6] Chen, J., Eberlein, L., Langford, C.H. (2002),
Pathways of Phenol and Benzene
Photooxidation Using TiO2 supported on A
Zeolite, Journal of Photochemistry and
Photobiology, Vol. 148, hal 183 -189.
[7] Chun, S.W., Jang, J.Y., Park, D.W., Woo, H.C.,
dan Chung, J.S. (1998), Selective Oxidation
of H2S to Elemental Sulfur Over TiO2/SiO2
Catalysts,
Applied
Catalysis
B
:
Environmental , Vol. 16, hal. 235243.
[8] Corma, A., dan Garcia, H. (2002), Lewis Acid
as Catalysts in Oxidation Reaction: From
Homogenous to Heterogenous System,
Chemical Review, Vol. 102, hal 3837-3892.
[9] Contsantine, M., Popa, J.M., dan Gubelmann.
(1993), Hydroxylation of Phenols/Phenol
Ethers, (US.Patents 5.254.746).
[10] Drago, R. S., Dias, S. C., McGilvray, J. M.,
dan Mateus, A. L. M. L. (1998), Acidity
and Hydrophobicity of TS-1, Journal of
Physical Chemistry, Vol. 102, hal. 15081514.
[11] Esposito, A., Taramasso, M. and Neri, C.
(1983).
Hydroxylating
Aromatic
Hydrocarbons. (US Patent No. 4,396,783).
[12] Huang, D.G., Liao, S.J., Liu, J.M, Dang, Z.,
dan Petrik, L. ( 2006), Preparation of
Visible- Light Responsive N-F-codoped
TiO2 Photocatalyst by A Sol Gel
Solvothermal
Method,
Journal
of
Photochemistry and Photobiology, Vol. 164,
hal 242-266.
[13] Indrayani, S. (2008), Aktivitas Katalitik
menggunakan H2O2 , Tesis M.Sc., Jurusan
Kimia, FMIPA Institut Teknologi Sepuluh
Nopember, Surabaya.
[14] Kung. H. H. (1989), Transition Metal Oxides:
Surface Chemistry and Catalysis, Study
Surface Science and Catalysis. 45.
[15] Lamberti, C., Bordiga, S., Zecchina, A.,
Artioli, G., Marra, G. and Spano, G.,
(2001), Ti Location in the MFI Framework
of Ti-Silicalite-1: A Neutron Powder
Diffraction Study. Journal of Am. Chem.
Soc., Vol. 123, hal. 2204-2212.
[16] Li, G., Wang, X., Guo, X., Liu, S., Zhao, Q.,
Bao, X., and Lin, L. (2000). Titanium
Species in Titanium Silicalite TS-1 Prepared
576

January 24, 2009
ISBN : 978 979 19201 0 0
By Hydrothermal Method, Materials

chemistry and Physics, Vol. 71, hal 195201.
[17] Machado, N.R.C, dan Santana, S.V. (2005),
Influence of Thermal Treatment on The
stucture and Photocatalytic Activity of TiO2
P25, Catalysis Today, Vol 107-108, hal.
595-698.
[18] Nur, H., Prasetyoko, D., Ramli, Z., Endud, S.
(2004), Sulfation: A simple Method to
enhance the Catalytic Activity of TS-1 in
Epoxidation of 1-octene with Aqueous
Hydrogen
Peroxide,
Catalysis
Communications . Vol.5, hal. 725728.
[19]
Nur,
H.,
(2006),
Heterogeneous
Chemocatalysis: Catalysis by Chemical
Design, Ibnu Sina Institute for Fundamental
Science Studies Universiti Teknologi
Malaysia, Johor Bahru.
Proceeding Book
577

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Improved Properties of SnTiO3 Thin Film Light Sensor

Prepared by Sol-Gel Method
Tulus Ikhsan Nasution1,2*, Zaliman Sauli1, Hasnizah Aris1 and Eddy Marlianto2
1
School of Microelectronic Engineering

Universiti Malaysia Perlis, 02600 Kangar, Perlis, Malaysia
2
Faculty of Mathematics and Natural Sciences
Universitas Sumatera Utara, Medan 20155, Indonesia
*e-mail ikhsan@unimap.edu.my
Abstract
Thin films based on SnTiO3 sensing material have been successful to deposit on the silicon
(Si) substrates. The films were annealed at 700oC in air for 30 s. The surface roughness of
the films was observed by using an Atomic Force Microscopic (AFM). The current-voltage
characteristics were measured at the relative low positive voltages under the condition
without and with light exposure. It was found that the electrical currents of SnTiO3
composite are higher compared with those of single phase SnO2 both without and with light
exposure. The improved properties of SnTiO3 composites are related to its smoother
surface and smaller grain size than SnO2.
Keywords: Thin film, Sensitivity, Sol-gel, Tin dioxide, Tin Titanate
Introduction
Tin dioxide (SnO2) has been well known as a high
performance n-type semiconductor with a large band
gap. Thus, light will be easy to penetrate into this
material and generate the free carriers [1-2]. An
improvement of the electrical properties can be done
if the semiconductor oxide adsorbs the light because
the adsorption can result in a photoexcitation,
affecting the charge transport across the grain
boundaries [3]. This provides an advantage which
enables the sensors based on semiconductor oxide
have high performance. However, a strong demand of
the commercial market for reliable and low cost
sensors leads to the need of continuously developing
new sensing materials with the improved properties.
The sensor fabrication in small size is also to be
important work because it makes easy to integrate it
into an electrical circuit [4].
Many methods can be utilized to produce a variety
of new sensing materials, especially including
chemical processes. In this work, sol-gel method is
considered to be the most suitable method to prepare
SnTiO3 composite as a sensing material due to this
method offers some significant advantages such as
purity and homogeneity that can be obtained by the
distillation. The low capital cost of the equipment and
simplicity make it an excellent technique for
formulating new compositions [5-6].
The electrical conductance of SnTiO3 thin film
sensors are examined under light exposure (photo
current) and no light exposure (dark current) to
Proceeding Book
investigate the effect of light intensity to the

photocurrent. The characterizations of its structural
and electrical properties are also carried out to explain
an important role of grain size distribution, grain
boundaries and surface state in increasing the
sensitivity of SnO2-TiO3 thin film sensors.

Tin acetate [Sn(CH3COO)2] and titanium
isopropoxide [Ti(OC3H7)4] were used as starting
materials to prepare the precursor solution of SnTiO3.
The 2-methoxyethanol (2-MOE) was used as a
solvent. Titanium isopropoxide was dissolved in the
2-MOE, then tin acetate was added into the titanium
solution. After agitating the mixture of tin-titanium
(Sn-Ti) in 2-MOE for 4 hours, Sn-Ti complex
solution was obtained.
The precursor solution was then spin-coated onto
Al/SiO2/Si substrate at 3000 rpm for 30 s. The spincoated wet films were pre-baked at 90oC for 30
minutes over a hot-plate to remove the organic
contaminations. This procedure was performed
several times to obtain the appropriate thickness. The
films were final-annealed at 700oC for 15 s in a rapid
thermal annealing processor. The surface roughness
and grain size of SnO2 and SnTiO3 thin films were
characterized by atomic force microscope (AFM).
The current-voltage (I-V) measurements of the SnO2
and SnTiO3 thin films were carried out by using
semiconductor parametric analyzer (SPA) from 0 to 1
V in air.
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Figure 1 (a) and (b) show the three-dimensional

micrographs of SnO2 and SnTiO3 thin films deposited
by using a sol-gel deposition technique. The AFM
observation was carried out in contact mode with a
scan area of 5000 nm x 5000 nm and a scan speed of
2 Hz. The micrographs indicate that SnTiO3 has the
smoother surface roughness compared with SnO2.
800
SnO2 (Without Light)
SnO2 (With Light)
700
SnTiO3 (Without Light)

SnTiO3 (With Light)
600
Current (mA)
their surface. The similar results are obtained for

repeated measurement.
500
400
300
200
100
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Voltage (V)
Fig. 2: I-V curves for SnO2 and SnTiO3 thin films.
Fig. 1
Three-dimensional AFM images of the

surface of the BST thin film pre-sintered at
(a) 400oC and (b) 600oC.
This is evident from the three-dimensional
micrographs, where the z-scale range increased from
100 nm (Fig. 1 (a) to 150 nm (Fig. 1 (b). This is also
confirmed with the grain size of SnO2 decreased from
about 220 nm to about 95 nm. Beside that, no
microcracks are observed on the surface of both films
that enables to get the reliable data when the electrical
measurement is repeated.
The addition of Ti elements into SnO2 caused the
grain growth rate to be slower during annealing
process. The degree of roughness is represented by
mean roughness which is the mean value relative to
the centre line or plane. The surface area difference is
defined as a percentage increase in a comparison of
the 3-dimensional surface area produced by
projecting the surface onto the threshold plane. The
mean grain size is statistically calculated from the
total number of grains [7].
Figure 2 shows the behavior of electrical current
of SnO2 and SnTiO3 thin films without and with light
exposure as a function of varying voltages. The
currents increased steeply with increasing the applied
voltage up to around 0.55 V and above 0.55 V, the
current increased modestly with the increase of the
applied voltage. The current difference between SnO2
and SnTiO3 is less without light illumination.
Whereas under light illumination, SnTiO3 shows
higher current values compared with SnO2. This
result indicates the Ti elements in SnO2 is surely
acting as a light absorbing elements. The
measurements were done under the constant energy
irradiation. It was also found that both SnO2 and
SnTiO3 have fast response to the light that falls on
Proceeding Book
Fig 3. The sensitivity of SnO2 and SnTiO3 to the light

Comparing the current values under light
illumination and without light illumination provides
the sensitivity values as depicted in Figure 3. It was
found that the sensitivity of SnTiO3 is higher than that
of SnO2. It is believed that the increase in sensitivity
of SnO2 with the incorporation of Ti element is
affected by the reduction of particle size which causes
SnTiO3 is to be more porous compared with SnO2.
Therefore, the higher sensitivity of SnTiO3 is ascribed
to an enhancement of light adsorption by the light
confinement within porous SnTiO3 layer as
previously reported for porous TiO2 thin film [8]. The
Ti activities in light adsorption or the change in
Fermi-level can be considered to be responsible for
the increased sensitivity. However, the further
investigations are needed to prove the correctness of
these preliminary expectations.
Conclusion
The conclusion of this study can be summarized as
the following:
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The addition of Ti element into SnO2 structure has an

effect to increase its electrical current and in turns,
causes the sensitivity of SnTiO3 is higher compared
with that of SnO2. It is believed that the smoother
surface roughness of SnTiO3 than SnO2 plays an
important role for the improved electrical properties.
Adding the thickness of the films is believed can
increase the sensitivity to be much higher from the
present results.
[8]
Okuya, M., Shiozaki, K., Horikawa, N.,

Kosugi, T., Kumara, G. R. A., Madarasz, J.,
Kaneko, S. and Pokol, G. 2004. Porous TiO2
thin films prepared by spray pyrolysis
deposition (SPD) technique and their
application to UV sensors, Solid State Ionics,
172, 527-531.
Acknowledgements
The financial support from Universiti Malaysia Perlis
(UniMAP), Universitas Sumatera Utara (USU) and
FRGS 9003-00184 is greatfully acknowledged.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
Nishikawa, S., Hashimoto, H., Chikamoto, M.,

Horikoshi, K., Aoki, M., Arima, K., Uchikosi,
J. and Morita, M. 2006. Photo current through
SnO2/SiC/p-Si(100) structures, Thin Solid
Films, 508, 385-388.
Wu, C. L., Chou, J. C., Chung, W. Y., Sun, T.
P. and Hsiung, S. K. 2000. Study on
SnO2/Al/SiO2/Si ISFET with a metal light
shield, Materials Chemistry and Physics, 63,
153-156.
Comini, E, Faglia, G. and Sberveglieri. 2001.
UV light activation of tin oxide thin films for
NO2 sensing at low temperatures, Sensors and
Actuators B, 78, 73-77.
Nasution, T. I, Sauli, Z. and Omar, R. 2006.
Electrical and sensing properties of
SnO2(4mol%ZnO)/CuO(4mol%ZnO) heterocontact gas sensor having the sensitivity to CO
gas, Proceedings of the International
Conference on Mathematics and Natural
Sciences (ICMNS), Bandung, Indonesia, ISBN
979-3507-91-8.
Nasution, T. I., Zaliman, Johari, Azhar, Z.,
Taking, S. Hikam, M. N. and Idris, M. A. 2007.
Effect of Pre-Sintering Temperature on the
Electrical Properties of Ba0.5Sr0.5TiO3 Thin
Films Derived from a Solution Deposition,
Proceedings of IEEE Regional Symposium on
Microelectronics, ISBN 9-789839-933543.
Nasution, T. I., Zaliman, Johari, Azhar, Z.,
Taking, S. Hikam, M. N. and Idris, M. A. 2007.
The Electrical Properties of Ba0.5Sr0.5TiO3 Thin
Films to the Different Temperatures,
Proceedings of IEEE Regional Symposium on
Microelectronics, ISBN 9-789839-933543.
Cantalini, C., Pelino, M., Sun, H. T., Faccio, M.,
Santucci, S., Lozzi, L. and Passacantando, M.
1996. Cross sensitivity and stability of NO2
sensors from WO3 thin film, Sensors and
Actuators B, 35-36, 112-118.
Proceeding Book
580

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Application of Chitin and Chitosan Isolated from Waste of

Java Sea White Shrimp (penaeus merguensis) as Adsorbent
Khabibi, Rum Hastuti, Sri Syufaati
Department of Chemistry, University of Diponegoro
Abstract
Research of adsorption rhodamine by chitin and chitosan that isolated from waste of java sea white
shrimp (penaeus merguensis) have been done. The purpose of this research is to isolate chitin from
the waste of white shrimp skin, transformation of chitin to chitosan, and that application as adsorbent
rhodamine in pH, time of optimum contact and determine the maximum adsorption capacity of
rhodamine. Chitin was isolated from waste of java sea white shrimp (penaeus merguensis) through
deproteination, demineralization, and depigmentation processes. transformation of chitin to chitosan
through deacetylation processes. Chitin and chitosan usage as adsorbent of rhodamine is conducted
in pH variation of 2, 3, 4, 5, 6, 7, 8, and 10, contact time of 15, 30, 45, and 60 minutes. Concentrate of
60, 120, 180, 240, and 300 ppm with volume of sample 20 ml, stiring speed 150 rpm and the amount
of chitin/chitosan 1 g. Analysis of chitin and chitosan using FTIR spectrometer to determine the
groups that found on chitin and chitosan. The quantity residu of rhodamine which not adsorb by chitin
and chitosan were analyzed usely UV-Vis, while to determine the maximum adsorption capacity
using the Langmuir isotherm equalization.
The result of extraction is gained white-colour chitin and white-grayish chitosan obtained contained
70.48%. The optimum adsorption pH of chitin into rhodamine occurs in pH of 5 and the optimum
adsorption of chitosan into rhodamine in pH 3. Time of adsorption optimum contact of rhodamine by
chitin and chitosan occurs in 30 minutes. The maximum adsorption capacity chitin of rhodamine 5.69
mg/g and the maximum adsorption capacity chitosan of rhodamine 6.55 mg/g. it is concluded that
chitosan more effective as adsorbent rhodamine than chitin.
Keywords: chitin, chitosan, adsorption, rhodamine, white shrimp
Introduction
Rhodamine is one of dye that used widely for
papers, textile and snacks industries (Isminingsih,
1973). Rhodamine is resistant to sunlight effect and
difficult to be degraded biologically because its
relative stable aromatic structure. Rhodamine waste
is very dangerous for human life because it can be
accumulated in a body and cause liver cancer.
(C2H5)2N
fodder or food industry such as shrimp chips

(Benjakul and Shophanodora, 1993).
Shrimp shells contains chitin (Muzzarelli 1985)
functioning as adsorption of organic compound and
pigment substance because chitin has amide bunch
(-NHCO) and Hydroxyl bunch (-OH) as active site.
Chitin can be isolated from shrimp shell through
de-proteinasi, demineralization, and depigmentation
processes.
CH2OH
N+(C2H5)2Cl-
CH2OH
O
H
H
OH
OH
H
COOH
H
NHCOCH3
NHCOCH3
kii
Figure 1. Structure of Rhodamine

Besides waste from dyeing at textile, there
is another source of Rhodamine waste that is from
shrimp processing as an export commodity in a
form of shrimp without head and shell so that the
shrimp waste are head and shell of shrimp as
additional product.
North Java Ocean as a shrimp producer
produces more than 50 thousand tons a year.
Shrimp producing produces shrimp waste that is
30-40 % from the whole shrimp weight (Moeljanto,
1984). Since now, shrimp shell waste uses for
Proceeding Book
Figure 2. Structure of Chitin
Chitin can be changed into chitosan

through deasitilasi, that causes N-acetyl released so
that it changes an unit of N-acetyl glucosamine into
an unit of glucosamine (Robert, 1992) because
chitosan has amine bunch (-NH2) and Hydroxyl (OH) as active bunch so that chitosan can be used as
adsorbent either organic or inorganic compounds.
CH2OH
CH2OH
O
H
H
OH
H
O
H
OH
NH2
H
H
NH2
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Figure 3. Structure of Chitosan

Filipkowska (2007) had used chitin as
adsorbent of black 8 and black 5 colors with
optimum adsorption at pH 6 while Chiou et al
(2003) argued that chitosan can be used as pigment
substance of AAVN (Acid Alizarin Violet N) and
RB4 (Reactive Blue 4) at pH 3. Setyadi (2005) was
made chitosan as pigment adsorbent of indigo
carmine through chromatography method with
maximum adsorption chitosan toward indigo
carmine at pH 4. Indigo carmine, AAVN, RB4 and
Rhodamine have similar structure. Those are
aromatic compounds. Thus, Rhodamine is expected
capable to be adsorbed by chitin and chitosan. The
objective of this research is to isolate chitin from
white shrimp shell waste, from Java sea, and
transform to be chitosan, and determine its effect as
rhodamine adsorbent.
Rhodamine adsorption by chitin and chitosan with

various time-contacts
Each of 4 Erlenmeyer is added with 20 ml of 60
ppm Rhodamine and a gram of Chitin/ Kitosan at
optimum pH and then shakes with bath shaker for
15, 30, 45 and 60 minutes. The solution, the result
of adsorption, is measured quantitatively using
spectrophotometer UV-vis at 570 nm.
Rhodamine adsorption by chitin and chitosan with
various concentration.
Rhodamine solution in different concentration: 60,
120, 180, 240, and 330 ppm is added with a gram of
chitin/ chitosan then shake using bath shaker at
optimum time and pH. The solution, the result of
adsorption, is measured quantitatively using
spectrophotometer UV-vis at 570 nm.
Materials
Chitin and chitosan Extraction
Dry white shrimp (penaeus merguensis) shell

powder from java sea, NaOH (p.a merck), HCl (p.a
merck), H2O2 (p.a merck), citric acid (p.a merck),
Na2HPO4 (p.a merck).
Chitin subtracts from shrimp shells by doing chitin

extraction from shrimp shell powder through
process of de-proteinasi, demineralization while to
get chitosan can do by deasetilasi process. Deproteinasi process can cause the bunch of protein
and chitin released. Demineralization is the process
of the elimination toward mineral of shrimp shells.
Mineral of shrimp shells is CaCO3. Thus, using
HCL, the mineral of shrimp shells can be
eliminated because the forming of CaCl2 that can be
eliminated. The equation of reaction is:
2HCL + CaCO3 CaCl2 + H2CO3
De-pigmentation process is a process to eliminate
pigment so that it becomes white residue. The depigmentation is a process using 3% of H2O2 that
functioning as strong oxidant. The result of
extraction is gained white-colour chitin. The final
residue outcome is Chitin and analyzed using
spectrosphometer FTIR, with result as in Figure 1.
Chitin and Chitosan Extraction

Two hundred grams of dry shrimp shell powder is
added by a liter of 3,5 % NaOH, then heat at 65C
for 2 hours along mixing. Then, the mixture is
filtered and washed by aquades. Residue is added to
HCL 1 N heated at temperature of 65C for 2 hours.
Residue is put at 250 ml of 3% H2O2 for 24 hours
by 2 times of soaking. The mixture is filtered and
residue is washed by aquadest then dried by oven at
80C for 8 hours of chitin purifying process.
Chitin transformation to become chitosan:
Residue is added by 500 ml of 50 % NaOH solution
then heated at 100C for 2 hours with mixing. The
mixture is filtered and residue is washed by
aquadest until neutral. The residue is dried at 80C
for 8 hours to get chitosan powder. Characterizing
of result (Chitin and chitosan) is analyzed using
spectrophotometer FTIR.
Rhodamine adsorption by chitin and chitosan
with various pH
A gram of chitin/ chitosan powder put in
Erlenmeyer. Then, 20 ml solution of 660 ppm
Rhodamine sample with various pH i.e.
2,3,4,5,6,7,8 and 10 is added into it and shake it by
bath shaker during 30 minutes, room temperature.
The solution, the result of adsorption, is measured
absorbency using spectrophotometer UV-vis at 570
nm.
Proceeding Book
Figure 4. Spectra FTIR of chitin
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Table 1 Wave number and prediction groups

funtional in chitin
Wave Number (cm- Prediction funtional
1
)
groups
3443,74
Stretching N-H
overlapp O-H
2927,05
Stretching C-H
alifatik
1653,11
Stretching C=O
1559,87
N-H sekunder
1379,34
Stretching CH3
1157,14
Stretching C-O eter
1073,26 dan
Stretching C-N
1029,62
rhodamin by chitin and chitosan for 30 minutes. In

chitin rhodamine adsorption more increases
significantly at pH 2-5. After pH 5, colour essence
of rhodamin that been adsorbed more decreases,
rhodamine adsorption in chitin occurs because of
interaction of amide group that being proton by N+
group from rhodamine.
Figure 3 correlation between Rhodamine that

adsorbed (q) chitin with pH
Figure 5. Spectra FTIR of chitosan

Table 2 Wave number and prediction groups
funtional in chitosan
Prediction funtional
Wave Number (cm-1)
groups
3442,91
Stretching N-H overlapp
O-H
2922,39
Stretching C-H alifatik
1652,98
Stretching C=O
1558,51
Stretching N-H
1034,98
Stretching C-N
Obtained Chitin is then deasetilated, is a
process of reducing acetyl (-COCH3) groups
substituted with hydrogen groups so that amide (NHCOCH3) change to amina (-NH2) group
(Tokura,1995). Deasetilation degree is determined
by base line method and obtained 70,48%.
The result of deasetilation is white-grayish chitosan
Analysis outcome of chitosan Spectra FTIR (Figure
2), show correspondence of some groups chitosan
function according to Sastrohamidjojo, 1991;
Khopkar, 1990; and Fessenden, 1992. Chitosan
function groups resulted in Spectra FTIR seen in
Table 2.
Figure 4 correlation between Rhodamine that

adsorbed chitosan (q) with pH
Figure 4 shows that rhodamine adsorption
by kitosan. At pH 2-3 more increases, but after pH
4 color essence of rhodamine that being adsorbed
decreases. This is because chitosan has amina
(NH2) groups that has one set of dependent electron
in atom N. This amina group serves as lewis base
by sharing its set of dependent electron, so that at
pH acid/base will enable protonation very
small/even doesnt occur. According to Suhardi
(1993) that amina groups at chitosan, can fasten
color essence because chitosan has character of
cationic so that in acid condition amina groups
(NH2) will be protoned become (NH3+). The more
increasing of rhodamin that is adsorbed, the more
many amina groups that is protoned (Chiou, 2003).
The Determination of Optimum pH of Rhodamine

Adsorption by Chitin and chitosan
The Determination of Optimum Contact Time

toward Rhodamine Adsorption by Chitin and
Chitosan
pH is one of factors that influence

adsorption process. From data of determination of
colour essence of rhodamine textile that been
adsorbed because of pH influence. Figure 3 shows
pH influence toward adsorption of color essence of
Study about this influence of contact time aims to

know optimum contact time at adsorption of color
essence of rhodamine by chitin and chitosan.
Contact time is varied from 15, 30, 45, and 60
Proceeding Book
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January 24, 2009
ISBN : 978 979 19201 0 0
minutes with compound volume 20 ml at pH 5

(chitin) and pH 3 (chitosan). In Figure 5 and 6 show
the influence of time toward rhodamin adsorption
by Chitin and chitosan. The longer contact time, the
more color essence that is absorbed by Chitin and
chitosan, then further occurs decreasing of
adsorption of color essence of rhodamin.
Figure 7 correlation between rhodamine that

adsorbed (q) by chitin with various
concentration of rhodamine
Figure. 5 correlation between contact time with
rhodamine that adsorbed by chitin (q)
Figure. 6 correlation between contact time with

rhodamine that adsorbed by chitosan
(q)
This shows that stability has been
achieved. And the adsorption tends to decrease after
it goes on for 30 minutes, probably it occurred
resulted in interaction of adsorben with adsorbat
that too much full. Contact time of 30 minutes
seems have the most optimum adsorption.
The Adsorption by Chitin and chitosan with
Variation of Rhodamin Concentration
Rhodamine adsorption by chitin and chitosan is
conducted by variation of concentration between
60, 120, 180, 240, and 300 ppm with pH 5 for
Chitin and pH 3 for kitosan during 30 minutes.
Maximum rhodamin adsorption by Chitin and
kitosan are 5.695 mg/g and 6.549 mg/g (based on
isotherm Langmuir equalization). At rhodamin
adsorption by Chitin can be seen from Figure 7 and
chitosan from figure 8, adsorbtion outcome shows
that increasing of chitosan adsorbing power occurs
with increasing of rhodamin solution concentration.
The bigger rhodamin concentration, kitosan power
tends to more increase, and at certain concentration
that results in equal condition thus the increasing of
concentration doesnt influence adsorbing power
anymore.
Proceeding Book
Figure 8. corelation between rhodamine that

adsorbed
(q) by chitosan with various concentration
of
rhodamine
According to Robert (1992) chitin has
NHCOCH3 (amida) active groups, and involves
interaction of hydroxyl (-OH) group as active site
that fasten the color essence and chitosan has either
hydroxyl (-OH) active groups or amina (NH2).
Interaction of Chitin and chitosan with
rhodamine can occur because of electrostatic
interaction (Longhinotti, dkk., 1998). Electrostatic
interaction of chitin and rhodamine due to a set of
dependent electron at N-amida (-NHCOCH3)
groups that is shared at N-rhodamine (N+-(C2H5)2)
groups, while electrostatic interaction at chitosan
because of groups from rhodamin -COO(Annadurai, 2002) and (-NH3+) positive groups at
chitosan. So that rhodamine adsorption by chitosan
more increases by more many amina groups that is
protoned (Chiou, 2003).
Result of the study shows alteration of the
color occurring after adsorption process. The color
of Chitin that is formerly yellowish-white changes
to red and the color of chitosan that is formerly
brownish-white changes to red. While rhodamine
solution is formerly red changes to more
transparent (bright). That alteration suggests that
rhodamine in the solution has been absorbed by
either chitin or chitosan.
584

January 24, 2009
ISBN : 978 979 19201 0 0
The prediction of interaction that occurs between
chitin and chitosan with rhodamine is:
Chitin-N (amida)+ +N(C2H5)2-rhod Kit-(amida)N +N(C2H5)2-rhod

Chitosan-NH3+ + -OOC-rhodKit-NH3+ + -OOC-rhod
Based on estimation using isotherm Langmuir

equalization, maximum capacity of rhodamin that is
absorbed by Chitin and chitosan is 5.695 mg/g and
6.549 mg/g. this suggests that chitosan is more
effective than chitin for adsorbing rhodamine.
Conclusion
The result of extraction is gained whitecolour chitin and white-grayish chitosan obtained
contained 70.48%. The optimum adsorption pH of
chitin into rhodamine occurs in pH of 5 and the
optimum adsorption of chitosan into rhodamine in
pH 3. Time of adsorption optimum contact of
rhodamine by chitin and chitosan occurs in 30
minutes. The maximum adsorption capacity chitin
of rhodamine 5.69 mg/g and the maximum
adsorption capacity chitosan of rhodamine 6.55
mg/g. it is concluded that chitosan more effective as
adsorbent rhodamine than chitin.
Kadmium, dan Tembaga) Di Perairan,

IPB, Bogor
Mekawati, Facriyah, E., and Sumardjo, D., 2000,
Aplikasi Kitosan Hasil Transformasi Kitin
Limbah Udang (panaeus merguensis)
untuk Adsorpsi Ion Logam Timbal, Jurnal
sains dan Matematika., vol. 8(2)
Moeljanto,1984, Penangkapan Ikan Segar, PT
Penebar Swadaya, Yogyakarta
Muzzarelli, R. A. A., 1985, Chitin, New York :
Pengaman Press
Robert, G. A. F.,1992, Chitin Chemistry, The
Macmillan Press, London
Sastrohamidjojo, H., 1991, Spektroskopi, Liberty,
yogyakarta
Suhardi, 1993, Khitin dan Khitosan, Yogyakarta :
PAU Pangan dan Gizi UGM
Tokura, S. and N.N, 1995, Specification and
Characterization of Chitin and Chitosan,
Collection
of
working
papers.28,
Universiti Kebangsaan Malaysia
References
Annadurai, G., 2002, Adsorption of Basic Dye on
Strongly Chelating Polymer: Batch
Kinetics Studies, Journal Iranian Polymer.
vol 11, no. 4
Benjakul, S. dan P. Shophanodora, 1993, Chitosan
Production from Carapace and Shell of
Black Tiger Shrimp, ASEAN food J.vol 8,
no. 4
Chiou, M., ho, P., dan Li, H., 2003, Adsorption
Behavior of Dye AAVN and RB4 in Acid
Solutions on Chemically Cross- Unked
Chitosan Beads, J.Chm. Inst. Chem, Engrs,
PP, Taiwan
Fessenden & Fessenden, 1991, Kimia Organik,
edisi ketiga, Erlangga, Jakarta
Filipkowska, U., 2007, Adsorpstion and desorption
Efficiency of Black 8 and Black 5 onto
chitin and chitosan, Polish Chitin Society,
Monograph XII, Olsztyn
Isminingsih, R., 1973, Pengantar Kimia Zat Warna,
ITB, Bandung
Longhinotti, E., Pozza, F., Furlan, L., de M, M. de
N.,
Sanchez,
Klug,
M.,
Laranjeira, M. C. M., and Favere, V. T.,
1998, Adsorption of Anionic Dyes on the
Biopolymer Chitin, J. Braz. Chem. Soc.,
Vol. 9, no. 5, Brazil
Marganof, 2003, Potensi Limbah Udang Sebagai
Penyerap
Logam
Berat
(Timbal,
Proceeding Book
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The First International Seminar on Science and Technology

January 24, 2009

Study of H-Zeolite Addition in The Esterification Step of Biodiesel Synthesis

molecules with an alcohol molecule attached to one

The First International Seminar on Science and Technology

purpose of the treatment is to reduce free fatty acids

Materials And Methods

Figure.1 Biodiesel reactor with capacity of 10 L to

Results And Discuccion

The First International Seminar on Science and Technology

The study was initiated with natural zeolite

could be concluded that the acid activation resulted in

Figure. 2 Difractogram of natural zeolite (above) and H-zeolit (below)

The First International Seminar on Science and Technology

Figure 3. FT-IR Spectra of H-zeolite (above) and natural zeolite (below)

Infra red analysis result also supported the

Figure 4. Used cooking palm oil (left) and biodiesel

The First International Seminar on Science and Technology

Figure. 5. Proton-NMR spectra of used cooking palm oil

Fig. 6. Proton-NMR spectra of esterification product

The First International Seminar on Science and Technology

Fig. 7. Proton-NMR spectra of biodiesel

major compound ca. 40.66% (Fig. 8-12). Other

Figure.8 Chromatogram of mixed methyl esters

The existence of methyl palmitic was indicated by the

264, 74, 69, 55 and 41 was caused by methyl oleic

The First International Seminar on Science and Technology

Figure 9. Mass spectra and structure of methyl palmitic

Figure 10. Mass spectra and structure of methyl linoleic

Figure 11. Mass spectra and structure of methyl oleic

The First International Seminar on Science and Technology

Figure 12. Mass spectra and structure of methyl stearic

The First International Seminar on Science and Technology

Arrowsmith, C.J., J. Ross, 1945, Treating

Houas, A. Lachleb, H., Puzenut, E., Ksibi,

The First International Seminar on Science and Technology

Preparation of Solid Acid Catalysts from Bentonite and Their Catalytic

Faculty of Agricultural Technology, University of Andalas Padang, Indonesia

Jatropha curcas, solid acid catalyst, esterification, acid-activated bentonite, FFA,

acids (FFA) and water in this feedstock results in the

The First International Seminar on Science and Technology

solid acid catalyst is more environmentally friendly

Materials and Methods

The First International Seminar on Science and Technology

Where ai is the initial acid number of the reactant

Alkali catalysed transesterification of jatropha oil

The collected oil layer was transferred to 250 ml

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Fig. 1. The XRD patterns of the natural and some of

Table 1 Physical parameter of bentonite and acid-activated bentonites.

The First International Seminar on Science and Technology

significantly after 6 hours esterification. The best

The First International Seminar on Science and Technology

Effect of esterification reaction time to convertion

from 60oC to 65oC and methanol to oil ratio from

to perform. The bottom layer of glycerol was

1. Acid activation and calcination on bentonite

The First International Seminar on Science and Technology

follows: reaction time 6 h, amount of catalyst

The First International Seminar on Science and Technology

Synthesis and Characterization of Al2O3/TS-1

hydrophilic character to form titanium-peroxo

The First International Seminar on Science and Technology

Material and Methods