Indo. J. Chem.

, 2011, 11 (3), 279 - 284 279

UTILIZATION OF RICE HUSK AS RAW MATERIAL IN SYNTHESIS OF MESOPOROUS

SILICATES MCM-41

Suyanta* and Agus Kuncaka

Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada University, Sekip Utara
Yogyakarta, Indonesia 55281

Received June 8, 2011; Accepted September 26, 2011

ABSTRACT

The research about synthesis and characterization of MCM-41 from rice husk has been done. Silica (SiO2) was
extracted from rice husk by refluxing with 3M hydrochloric solution at 80 °C for 3 h. The acid-leached rice husk was
filtered, washed, dried and calcined at 650 °C for 6 h lead the rough powder of rice husk silica with light brown in
color. Characterization was carried out by X-ray diffraction (XRD) and FTIR spectroscopy method. Rice husk silica
was dissolved into the sodium hydroxide solution leading to the solution of sodium silicate, and used as silica source
for the synthesis of MCM-41. MCM-41 was synthesized by hydrothermal process to the mixture prepared from 29 g
of distilled water, 8.67 g of cetyltrimethyl ammonium bromide (CTMAB), 9.31 g of sodium silicate solution, and
amount mL of 1 M H2SO4. Hydrothermal process was carried out at 100 °C in a teflon-lined stainless steel autoclave
heated in the oven for 36 h. The solid phase was filtered, then washed with deionised water, and dried in the oven at
100 °C for 2 h. The surfactant CTMAB was removed by calcination at 550 °C for 10 h with heating rate 2 °C/min. The
as-synthesized and calcined crystals were characterized by using FTIR spectroscopy, X-ray diffraction and N2
physisorption methods. In order to investigate the effect of silica source, the same procedure was carried out by
using pure sodium silicate as silica source. It was concluded that silica extracted from rice husk can be used as raw
materials in the synthesis of MCM-41, there is no significant difference in crystallinity and pore properties when was
compared to material produced from commercial sodium silicate.

Keywords: MCM-41, rice husk, silica

INTRODUCTION and high thermal stability results in various applications

of MCM-41. For examples, it can be used as a catalyst
Indonesia is one of the major countries in the rice itself or being a catalyst support as well as an ion
producing, whereby it generates abundance of waste exchanger [5,7]. MCM-41 was prepared originally by
known as rice husk, a thin but abrasive skin in nature hydrothermal reactions of silicate gels in the
covering the edible rice kernel. About 20% of the rice temperature range from 100-120 °C [5].
husk ash residues left after the combustion cause The pure silicate substances such as sodium
environmental problems due to the pollution of both silicate and tetra ethyl ortho silicate (TEOS) usually
water and air. On the other hand, rice husk can be were used as a silica source in the synthesis of MCM-
considered as a useful matter, which can be employed 41. Due to its high silica content rice husk has become
as raw materials in kinds of applications [1-3]. The rice a source for preparation a number of silicon
husk is largely composed of silica with small amounts of compounds such as mesoporous MCM-41[7]. By using
inorganic compounds. Previous research had shown that rice husk as the silica source in the synthesis of MCM-
pure silica can be obtained from rice husk by an acid- 41, the production costs can be reduced subsequently
leaching procedure and calcination at 600 °C under besides helping to overcome environmental pollution.
atmosphere pressure. HCl is most often used for acid From such viewpoints, here the authors report the
leaching [4-5]. The extraction of silica from rice husk by utilization of rice husk as source of silica in the
acid treatment provides more than 95% by weight of synthesis of mesoporous silicates MCM-41. The
amorphous silica [2,6]. product (denoted as RH-MCM-41) was characterized
MCM-41 is amorphous material consists of by XRD, FTIR and physisorption methods, and
uniformly and highly ordered network of silica with compared to MCM-41 synthesized from commercial
unidimensional and hexagonally shaped. The pore size sodium silicate by the same procedure (denoted as Si-
of the MCM-41 can be controlled from 2 to 10 nm by use MCM-41). The results showed that rice husk can be
of an appropriate surfactant as a template [5]. These used as raw material in the synthesis of MCM-41. The
outstanding characteristics such as high surface area crystallinity characterization and the pore properties of

* Corresponding author. Tel/Fax : +62-2747897510

Email address : suyantakimiaugm@yahoo.co.id

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280 Indo. J. Chem., 2011, 11 (3), 279 - 284

MCM-41 synthesized from rice husk were similar to husk silica was added dropped wise to the surfactant
those of MCM-41 synthesized from commercial sodium solution under vigorous stirring. After stirring for 30 min
silicate. a small amount of 1 M H2SO4 was added to those
mixtures to reduce the pH to 10.2 and stirred for 1 h.
EXPERIMENTAL SECTION The silica-surfactant gel found was hydrothermally
treatment at 110 °C in a teflon-lined stainless steel
Materials autoclave for 36 h. After cooling at the room
temperature, the resulting solid product was recovered
The materials used for the preparation of the by filtration on a Buchner funnel, washed with distilled
mesoporous silicates MCM-41 were: rice husk found water, and dried in the open air at 90 °C. Surfactant
from some rice huller industries in Bantul, Yogyakarta, was removed by calcining the as-synthesized product
Indonesia, sodium silicate (27% (wt) SiO2, 8% (wt) at 550 °C for 10 h with heating rate of 2°/min. In order
Na2O, 65% (wt) H2O), hydrochloric acid (HCl), to investigate the effect of silica source, the same
cetyltrimethyl ammonium bromide (CTMAB), sulfuric procedure was carried out by using commercial sodium
acid (H2SO4), sodium hydroxide (NaOH), and distilled silicate leading to Si-MCM-41.
water produced by Laboratory of Basic Chemistry
Universitas Gadjah Mada Yogyakarta, Indonesia. Characterization
Characterization of the powder phases and
Instrumentation determination of the phase purities in the calcined
MCM-41 samples were carried out by XRD (Shimadzu
The equipments used in this research included XD-3H) using nickel-filtered Cu Kα radiation
chemical laboratory glassware, 3X Shimadzu X-ray (λ = 1.5406 Ǻ). The samples were scanned from 1 to
diffractometer (XRD) with Cu-Kα radiation, and PC-8201 10° (2θ), where θ is the angle of incidence of the X-ray
Shimadzu Fourier Transform Infrared (FTIR) beam to the plane. The lattice parameter (a0) was
Spectrometer and NOVA Ver. 2.00 sorptiometer. calculated by formula: a0 = 2d100/√3, where d100 is the
interplanar spacing corresponding to the (100) Bragg
Procedure reflection. Infra-red spectra were recorded with a
Shimadzu-8201 PC FTIR Spectrometer from KBr
Preparation of silica from rice husk and Pellets (0.005 g sample with 0.1 g KBr). The specific
characterization surface area and pore diameter of calcined-MCM-41
The rice husk was washed thoroughly with water to were analyzed using a NOVA Ver. 2.2 sorptiometer, by
remove adhering dust and soil, and then dried at 120 °C apply the conventional Brunauer-Emmett-Teller (BET)
overnight. The water rinsed rice husk (100 g) and and Barrett-Joyner-Halenda (BJH) equations. The pore
500 mL of 3 M HCl solution were refluxed under stirring wall thickness was calculated by subtracting the pore
in a round-bottomed flask at 80 °C for 3 h. The mixture diameter from the lattice parameter (a0).
was filtered and the husk was washed with distilled
water several times until the filtrate was free from acid. RESULT AND DISCUSSION
The acid-leached husk was then dried at 120 °C
overnight and calcined at 650 °C for 6 h, with a heating Characterization of Silica prepared from rice husk
rate of 2 °C/min. The silica from rice husk was
characterized by FTIR and XRD method. Sample of silica extracted from rice husk was
rough powder with light brown in color. The FTIR
Synthesis of sodium silicate solution spectrum of sample was presented in Fig. 1, that
The solution of sodium silicate (Na2SiO3) was shows an intense asymmetric, symmetric stretching
prepared by mixing 4.0 g of rice husk silica with 1.25 g of and bending vibration for Si-O-Si bonds at wave
-1
NaOH pellet and 35 g of distilled water. The resulting gel numbers 1110, 798, and 478 cm respectively [8];
-1
mixture was heated and stirred for 2 h at 353 K. The whereas the absorption band at around 3425 cm
mixture was then cooled to room temperature. related to left water molecule [8]. The absorption band
-1
at around 960 cm is not detected. It reveals that there
Synthesis of RH-MCM-41 and Si-MCM-41 is no silanol group.
RH-MCM-41 was synthesised by hydrothermal Fig. 2 shows the XRD diffractogram of the sample
method as follows. CTMAB (8.67 g) and 29 g of distilled in the range of 2θ = 20-80°. There is no peak, except
water were mixed and stirred for 30 min. There after the broad hump around 2θ = 23°, indicates that the rice
9.31 g of sodium silicate solution prepared from rice husk silica is in amorphous phase [3].

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 Indo. J. Chem., 2011, 11 (3), 279 - 284 281

Fig 1. FTIR spectra of silica extracted from rice husk Fig 2. Diffractogram of silica prepared from rice husk

Fig 4. FTIR spectra of Si-MCM-41: (A) as-synthesized

Fig 3. FTIR spectra of RH-MCM-41: as-synthesized (A) and (B) calcined
and calcined (B)

Characterization of MCM-41 vibration of symmetric and asymmetric stretching O-Si-

O bridge respectively [8]. These bridges are the part of
FTIR Spectra silicates polymer formed in the hydrothermal treatment
Shown in Fig. 3 and Fig. 4 are the FTIR spectra of [9]. A broad absorption band in the hydroxyl region
-1
RH-MCM-41 and Si-MCM-41 respectively before and between 3000 and 3700 cm with a maximum in the
-1
after calcination in the wavenumber region of range of 3450-3500 cm was observed in both cases.
-1
400-4000 cm . No significant difference was observed in This band associated with stretching vibration of
the structure of RH-MCM-41 and Si-MCM-41. Si-O-H group in the framework perturbed by physically
The as-synthesized MCM-41 sample on both adsorbed water molecules [8]. Due to the emerge of a
figures shows well defined bands at about 2924 and lot of Si-O-H groups after calcination, the intensity of
-1
2854 cm corresponding to n-C-H and d-C-H stretching those absorption band was significantly increased. The
-1
vibration of surfactant molecules [8]. The broad bands band at around 964 cm is associated with symmetric
-1
around 3500 cm attributed to the silanols at the Si-O-H stretching vibration, while the band at around
-1
external surface and adsorbed water molecules, while 455 cm is assigned to a SiO4 bending mode. There is
-1
deformational vibrations of adsorbed molecules cause no an absorption bands at 2924 and 2854 cm
-1
the absorption bands at around 1635 cm . The band at assigned asymmetric and symmetric stretching
-1
717 cm is associated with vibrations by the organic vibration of -CH2-, respectively; attributed to the
template [8]. perfectly combustion of surfactant in the calcination
Based on the spectrum of calcined samples, both treatment. Those bands indicated that the
-1
of spectra exhibit sharp bands around 1080 cm and RH-MCM-41 and Si-MCM-41 was successfully
-1
1226 cm of wave number which characteristic for synthesized.

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Fig 5. XRD patterns of RH-MCM-41: (A) as-synthesized Fig 7. Nitrogen absorption-desorption isotherms of RH-
and (B) calcined-MCM-41 MCM-41

Fig 6. XRD patterns of calcined-RH-MCM-41 (A) and Fig 8. Nitrogen adsorption-desorption isotherms of
calcined-Si-MCM-41 (B) calcined-RH-MCM-41 and Si-MCM-41

X-ray Diffractogram synthesized sample and 26° for calcined sample),

Fig. 5 shows the XRD patterns of as-synthesized indicating contraction of the lattice. Contraction of the
and calcined-RH-MCM-41. It is seen that the calcined- lattice is caused by the removal of template and
RH-MCM-41 diffractogram exhibits three peaks which subsequent condensation of silanol (Si-OH) groups.
can be indexed as 100, 110, and 200 plane respectively; In Fig. 6 the XRD patterns of calcined-RH-MCM-
and 44.71 Ǻ of lattice parameter, a0 (calculated by 41 and calcined-Si-MCM-41 are compared. That figure
formula: a0 = 2d100/√3). It was in good agreement with shows the little dependence of quality of MCM-41 on
MCM-41 diffractogram reported by some previous the silica sources used. High quality of MCM-41 was
reseachers. The diffractogram of MCM-41 published by produced from both RHA and commercial silica. XRD
Beck et al. [5] displayed 4 peaks with 100, 110, 200, and of Si-MCM-41 shows a slightly higher in resolution and
210 of Miller Index and 45 Ǻ of lattice parameter. intensity resulted from slightly higher crystallinity than
Whereas Kresge et al. [8] reported MCM-41 that of RH-MCM-41. In addition, the calcined-RH-MCM-
diffractogram with 100, 110, 200, and 210 of Miller Index 41 shows a higher value in 2θ of the peak, indicated
and 40 Ǻ of lattice parameter. The main peak at 2-3° of that the sample has thinner in pore walls compared to
2θ assigned the ordered hexagonal structure of Si-MCM-41. It seems the purer commercial silica can
MCM-41, while the other weak peaks at 4-6° of 2θ polymerize by more perfectly than RH in the formation
attributed the highly ordered of the structure [5,10]. of pore walls.
Upon calcination in the air at 823 K for 10 h with
heating rate 2°/min., the intensity of the XRD peaks Nitrogen physisorption
increased by about 3 times compared to the as- Fig. 7 shows the nitrogen adsorption-desorption
synthesized RH-MCM-41. These results reflect that the isotherms of RH-MCM-41. According to IUPAC
degree of ordering was dramatically improved by classification, type IV isotherms are obtained for this
surfactant removal. In addition, after calcination 2θ of the material. It can be observed that a well-defined step
main peak shifts to a higher value (25.4° for as- occurs in the adsorption curve at a relative pressure

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Table 1. The pore properties of the sample

Specific surface Mean pore Latice Pore walls
area, SBET, diameter, dmp parameter, ao thickness, Wt
Sample 2
(m /g) (nm) (nm) (nm)
RH-MCM-41 (prepared from 903.423 3.276 4.414 1.138
rice husk silica)
Si-MCM-41 (prepared from 946.607 3.357 4.533 1.176
commercial silica)
RH-MCM-41 reported by 730 2.2 *) *)
Siriluk and Yuttapong (2005)
*) Not reported

P/P0 of 0.2-0.3 indicating the filling of framework- Due to its smaller in adsorption capacities, the isotherm
confined mesopores. The pore filling (by capillary of RH-MCM-41 gives lower adsorption values over the
condensation) for that sample is restricted to a narrow whole relative pressure range. For the Si-MCM-41, the
range of P/P0 = 0.2-0.3, which is a typical feature for adsorption step corresponding to nitrogen
mesoporous MCM-41 materials [11]. These results condensation in primary mesopores is shifted toward
coincide with the results of XRD patterns. higher relative pressure indicating the occurrence of
This isotherm exhibits three stages; the first stage larger pores in this material in compared to RH-MCM-
was a linear part going through the origin, which was 41. With increasing pores size the occurrence of pore
caused by monolayer absorption of N2 on the walls of condensation is shifted to higher relative pressures as
the mesopores (P/P0 < 0.20). The second stage was at expected from classical theories of pore condensation.
higher pressures, which the absorption in mesopores The knees for RH-MCM-41 isotherm are not as steep
leads to multilayer formation until condensation takes as that of Si-MCM-41. According to Zhao and Lu [11], it
place, giving a sharp increase in absorption volume. is reflecting that the first sample has a relatively
According to Zhao et al. [11] and Selvam et al. [12], the broader in pore size distribution than the other one.
P/P0 value at which the inflection starts (at ca. P/P0 = The pore properties of RH-MCM-41 and Si-MCM-
0.20) is attributed to the commencement of pore filling 41 in this research and RH-MCM-41 reported by Siriluk
from which the pore diameter can be roughly estimated. and Yuttapong [7] were presented in Table 1.
The sharpness in this step indicates the uniformity of the The specific surface area (SBET) was determined
pore size distribution. As the mesopores are filled, the by using Brunauer-Emmett-Teller equations from the
absorption continues on the external surface. The third linear section of the BET plot, i.e. in the relative
stage in the absorption isotherm was an almost pressure range (0.05-0.25). The mean pore diameter
horizontal part after the relative pressure P/P0 of ± 0.35, (dmp) was calculated from the N2 adsorption data, using
due to multi layer absorption on the outer surface of the the BJH (Barrett-Joyner-Halenda) method. The latice
particles [11,13]. The total mesopore volume was parameters (a0) were calculated by formula:
calculated from the amount of vapor adsorbed at a0 = 2d100/√3, where d100 is the interplanar spacing
P/P0 = 0.35; assuming that MCM-41 were then filled with corresponding to the (100) Bragg reflection. The wall
condensed liquid nitrogen in the normal liquid state. thickness (Wt) is calculated by subtracting the pore
The hysteresis loop is observed at relative diameter from the lattice parameter (a0). According to
pressure P/P0 of > 0.42. It is consistent with type H3 Table 1, there is no significant difference was observed
hysteresis and is characteristic of capillary condensation in the pore properties of MCM-41 prepared from RH
between lamellar particles or in solids containing slit- and commercial silica in this research. RH-MCM-41
shaped mesopores. According to Gusev et al. [14] there produced in this research has larger both in specific
are two possible explanations: condensation of the surface area and mean pore diameter than that of
nitrogen (a) in interparticle spaces and/or (b) in residual similar material reported by Siriluk and Yuttapong [7].
lamellar mesostructures which occur during the
templating mechanism which forms the hexagonal CONCLUSION
structure. The absence of hysteresis loops in the
capillary condensation range is an indication that the Silica prepared from rice husk can be used as raw
material possesses pores in a lower mesopore range materials in the synthesis of MCM-41. The pore
2
[15]. properties of the product are: 903.423 m /g of specific
In Fig. 8 the nitrogen adsorption-desorption surface area (SBET), 3.276 nm of mean pore diameter
isotherms of calcined-RH-MCM-41 and Si-MCM-41 are (dmp), 3.276 nm of lattice parameter (a0), and 3.276 nm
compared. It could be observed that both of samples of pore walls thickness (Wt). There is no significant
have similar in nitrogen adsorption-desorption curves. difference in crystallinity and pore properties when was

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284 Indo. J. Chem., 2011, 11 (3), 279 - 284

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silicate. Mesoporous MCM-41 Prepared from Rice Husk
th
Ash, The 8 Asian Symposium on Visualization,
ACKNOWLEDGEMENT Chaingmai, Thailand, 23-27 May 2005.
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