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Environ Geochem Health (2010) 32:261–266

DOI 10.1007/s10653-010-9292-z

ORIGINAL PAPER

Synthesis and characterization of Fe-MCM-41 from rice


husk silica by hydrothermal technique for arsenate
adsorption
Kitirote Wantala • Suthipong Sthiannopkao •

Bang-orn Srinameb • Nurak Grisdanurak •


Kyoung Woong Kim

Received: 23 May 2009 / Accepted: 30 September 2009 / Published online: 17 April 2010
Ó Springer Science+Business Media B.V. 2010

Abstract Rice husk (RH) agro-waste was used as a MCM-41, contact time, pH of solution, and initial
raw material for synthesizing mesoporous molecular arsenate concentration. It was found that HT-Fe-
sieves, MCM-41. The Fe-MCM-41 was prepared by MCM-41 at the Si/Fe mole ratio of 10 gave the highest
the hydrothermal technique (HT), resulting in a higher adsorption capacity. Arsenate adsorptionh. The
surface area and crystallinity than when prepared under adsorption capacity of HT-Fe-MCM-41 (Si/Fe = 10)
ambient conditions. In addition, a hexagonal structure was affected by the initial pH value and the initial
was clearly seen with hydrothermal technique (HT) arsenate concentration. The adsorption capacity was
preparation. The adsorption of arsenate by HT-Fe- highest at pH 3 and decreased thereafter with increases
MCM-41 was investigated. The factors studied affect- in the pH of solution value. The Langmuir model fit the
ing arsenate adsorption capacity were ferric content in arsenate adsorption isotherm well. The maximum
adsorption capacity for arsenate was 1,111 lg g-1.

Keywords Rice husk  HT-Fe-MCM-41 


K. Wantala  B. Srinameb  N. Grisdanurak
Department of Chemical Engineering, Faculty Hydrothermal technique  Arsenate 
of Engineering, Thammasat University, Adsorption
Pathumthani 10120, Thailand

S. Sthiannopkao (&)
International Environmental Research Center (IERC),
Gwangju Institute of Science and Technology (GIST),
261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712, Introduction
Republic of Korea
e-mail: suthi@gist.ac.kr
Rice husk has become an attractive source material for
N. Grisdanurak the preparation of silicon compounds due to its high
National Center of Excellence for Environmental silica content, about 30 wt% silica including organic
and Hazardous Waste Management: Faculty of components. Rice husk silica was extracted with HCl
Engineering, Thammasat University,
Pathumthani 12120, Thailand acid. The resulting silica product showed the amor-
phous silica’s purity as greater than 98 wt% (Chumee
K. W. Kim (&) et al. 2009). Sodium silicate prepared from rice husk
Department of Environmental Science and Engineering, silica can be used as a source of silica to synthesize
Gwangju Institute of Science and Technology (GIST),
Gwangju 500-712, Republic of Korea mesoporous materials such as MCM-41 (Grisdanurak
e-mail: kwkim@gist.ac.kr et al. 2003; Chiarakorn et al. 2007; Chumee et al.

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262 Environ Geochem Health (2010) 32:261–266

2009). The MCM-41, with one-dimensional hexagonal The present research focused on the preparation of
mesopores (2–50 nm) and high surface area ([750 m2 Fe-MCM-41 by loading ferric oxide by the direct
g-1), has attracted considerable interest for various hydrothermal technique into MCM-41 made from
applications, especially for gas adsorption (Grisdanu- rice husk silica. This was labeled HT-Fe-MCM-41,
rak et al. 2003; Chiarakorn et al. 2007). Chiarakorn and was prepared at Si/Fe mole rations of 3, 5, and
et al. (2007)synthesized MCM-41 using rice husk 10. The HT-Fe-MCM-41 was characterized by X-ray
silica under ambient conditions, which involved diffraction (XRD), transmission electron microscopy
stirring at room temperature for 48 h. The resulting (TEM), and surface analysis (BET) techniques. The
product showed wall thickness of 11.5 Å. On the other HT-Fe-MCM-41 was made to remove arsenate from
hand, Chumee et al. (2009) synthesized MCM-41 by a synthesized drinking water. The extent of adsorption
hydrothermal technique. The product showed a sig- was examined as a function of contact time, initial
nificant increase in wall thickness, to 15.1 Å. The arsenate concentration, initial pH of solution, and
MCM-41 synthesized under an ambient environment ferric content. Finally, the adsorption isotherm was
may not withstand harsh conditions well. However, a investigated.
hydrothermal gel production method might improve
the strength of the MCM-41 structure. Therefore, in the
present research, the hydrothermal technique was
Materials and methods
chosen for preparing MCM-41 for arsenate adsorption,
as this technique was expected to yield a hexagonal
Chemicals
structure with a greater wall thickness.
Arsenic is a persistent contaminant in groundwater
All chemicals were analytical grade and purchased
and drinking water in South Asian and South East
from Ajax Laboratory Chemical (Australia), Fluka
Asian countries such as India, Bangladesh, Vietnam,
(Spain), Riedal-Dehaen (Germany), Kanto Chemical
Thailand and Cambodia (Smedley and Kinniburgh
(Japan), Acros Organics (USA) and J. T. Baker
2002; Sthiannopkao et al. 2008). Arsenic is a
(USA); all were used as received. For batch adsorp-
carcinogenic substance which is predominantly pres-
tion experiments, a stock solution containing 1,000
ent as inorganic species in a natural water system.
mg l-1 of arsenate was prepared from Na2HAsO4
The removal of arsenic from aqueous systems has
7H2O. The concentration of arsenate species was given
been studied widely and by many methods. Adsorp-
as elemental arsenate concentration in this study.
tion is relatively well known, uses inexpensive
materials, and is comparatively cost-efficient under
operation. Several adsorbents have been extensively Preparation of the Fe-MCM-41
experimented with for arsenic removal. These include
iron oxide-coated sand, ferrihydrite (FH), Al2O3/ The ferric-loaded MCM-41 was prepared according
Fe(OH)3, iron oxide-coated cement, Fe3? impreg- to the following procedures: first, a 4.50-g portion of
nated activated carbon, and iron oxide-loaded slag. hexadecyltrimethyl-ammonium bromide (CTAB) was
The results of these experiments reveal that loading transferred into 90 ml of deionized water in a Teflon
the ferric oxide into the adsorbent increased the beaker. Sodium silicate was prepared in another
adsorption capacity. Tong-on et al. (2009) looked at container by dissolving 5.00 g of NaOH in 30 ml of
adsorption of arsenic by ferric oxide loaded onto deionized water. Then, 3.00 g of rice husk silica and
MCM-41 and prepared under ambient conditions at FeCl3 at differing Si/Fe mole ratios (3, 5, and 10) were
mole ratios of Si/Fe 100, 50, and 10. For arsenate added. Next, the solution was stirred vigorously until
adsorption, results showed a trend for adsorption it was clear and viscous. The CTAB alkali solution
capacity increasing as the ferric content was raised. was poured into the prepared sodium silicate. The
Although the Si/Fe mole ratio of 10 gave the highest mixture was adjusted to make its pH 11. Then, the gel
adsorption capacity, it had a low surface area (342 m2 was aged in the autoclave at 100°C for 3 days. After
g-1), and the surface morphology of RH-Fe-MCM-41 aging, the suspended solid was filtered, and then
did not clearly show a hexagonal structure (Tong-on washed with deionized water and ethanol, dried in an
et al. 2009). oven overnight and calcined in the furnace at 550°C

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Environ Geochem Health (2010) 32:261–266 263

for 6 h under airflow. The adsorbent product was thus was clearly observed that, as more ferric was
obtained. The characterization of HT-Fe-MCM-41 incorporated, less major peak intensity occurred; also
was done by X-ray diffraction (XRD), transmission noted was the disappearance of the other three minor
electron microscopy (TEM), and surface analysis peaks. This clearly indicates that increasing ferric
(BET) techniques. content affected the structure of MCM-41 by hinder-
ing the crystallization process. It is generally agreed
that, for the synthesis of high-silica molecular sieves,
Research into HT-Fe-MCM-41 for removal
the more ferric content in the gel, the more difficult
of arsenate in aqueous solution
its crystallization becomes (Zhang et al. 2005). The
ferric is seen to cause an irregular hexagonal structure
Effects of the factors of ferric content in MCM-41 (3,
in MCM-41 by reducing gel stability, leading to a
5, and 10), contact time, initial pH of solution, and
badly built hexagonal array.
initial arsenate concentration were investigated, as was
From Fig. 1, it seems the structure of HT-Fe-
the adsorption isotherm. The solution was analyzed for
MCM-41 maintains hexagonality with a Si/Fe mole
residual arsenate by hydride atomic absorption
ratio of up to 5. However, HT-Fe-MCM-41 with a Si/
spectrophotometer (HD-AAS), Perkin Elmer series
Fe mole ratio of 10 had crystallinity of its MCM-41
AAnalyst 800, USA. The HD-AAS was calibrated by
much higher than at the Si/Fe mole ratio of 5. The
external standards technique. All samples were mea-
figure reveals that the crystallinity of HT-Fe-MCM-
sured at least twice in order to assess the reliability of
41 at the Si/Fe mole ratio of 10 was indeed obvious,
measurements.
particularly when compared to RH-Fe-MCM-41
synthesized in ambient conditions (Tong-on et al.
2009).
Results and discussion Figure 2a shows photographs of HT-Fe-MCM-41
taken by transmission electron microscopy (TEM).
Characterization and morphology At the mole ratio of Si/Fe 10, HT-Fe-MCM-41
of HT-Fe-MCM-41 clearly appeared in a hexagonal structure. However,
this hexagonal structure disappeared as the ferric
The crystallinity of HT-Fe-MCM-41 was evaluated content in MCM-41 was increased. The TEM results
by X-ray diffractograms, using CuKa radiation in an accord with the XRD results in explaining the
angular range (2h) from 1 to 30° with 40 mA and influence of ferric on hexagonal structure formation
40 kV. Peak appearance was found at (100), (110), in MCM-41. The TEM results, displayed in Fig. 2a
(200), and (210) hexagonal symmetry, as shown in and b, show a clear hexagonal structure in the HT-Fe-
Fig. 1. When ferric content (Si/Fe) was increased, it MCM-41 prepared by the hydrothermal technique.
This structure is far less apparent in the Fe-MCM-41
prepared under ambient conditions.
100
The porosity of adsorbent materials determined by
Brunauer Emmett Teller (BET) is summarized in
Table 1. The surface areas of HT-Fe-MCM-41 for the
Intensity (A.U.)

Si/Fe mole ratios of 3, 5, and 10 were 249.83, 518.40,


110
and 653.08 m2 g-1, respectively. The apparent trend
200 for the point of ferric content was that as ferric
210 (a) HT-Fe-MCM-41 (10)
content was raised, the surface area decreased. The
(b) HT-Fe-MCM-41 (5) same explanation of ferric content influence on the
(c) HT-Fe-MCM-41 (3) formation of a hexagonal structure in MCM-41 can
also be applied. At the Si/Fe mole ratio of 10, it was
0 5 10 15 20 25 30 found that the surface area of Fe-MCM-41when
2 Theta
prepared by the hydrothermal technique was twice
Fig. 1 XRD patterns of HT-Fe-MCM41 produced by applying as high as when Fe-MCM-41 was prepared under
the hydrothermal technique ambient conditions.

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264 Environ Geochem Health (2010) 32:261–266

160

Adsorption capacity (µg g )


-1
140

120

100

80

60

40

20

0
HT-Fe-MCM-41 (10) HT-Fe-MCM- 41 (5) HT-Fe-MCM-41 (3)

Fig. 3 Adsorption capacity of arsenate by HT-Fe-MCM-41 at


different mole ratios of Si/Fe

1200

Adsorption capacity (ug g )


-1
1000

800

600

Fig. 2 Photographs of HT-Fe-MCM-41 (a) and RH-Fe-MCM- 400


41 (b) at the mole ratio of Si/Fe 10 taken by TEM technique
200

0
Table 1 Surface area of HT-Fe-MCM-41 characterized by the 3 6 9 12
BET technique pH
Samples (mole ratio Mole ratio SBET Fig. 4 Effect of pH on adsorption capacity of arsenate
of Si/Fe) Si/Fe (m2 g-1)

HT-Fe-MCM-41 (3) 3 249.83 selected for use in the subsequent experiments on


HT-Fe-MCM-41 (5) 5 518.40 adsorption effects.
HT-Fe-MCM-41 (10) 10 653.08 Secondly, to assess the effect of initial solution pH,
RH-Fe-MCM-41 (10) 10 342.00 2 g l-1 of adsorbent was used in a 15-ml solution with
(Tong-on et al. 2009) an initial arsenate concentration of 2.0 mg l-1. The
solution pH values used were 3.0, 6.0, 9.0, and 12.0.
Adsorption of arsenate on HT-Fe-MCM-41 The results are shown in Fig. 4. It was found that the
highest adsorption capacity was 1,000 lg g-1 at pH 3,
The effects of ferric content, contact time, initial and the lowest adsorption capacity was 134 lg g-1 at
solution pH, and initial arsenate concentration on the pH 6. The adsorption capacity slightly increased with
adsorption of arsenate were examined. increases in pH, in the range between 6 and 12. At pH
Investigated first was the effect of the ferric content (at 3, arsenate may be removed by the reaction between
Si/Fe molar ratios of 3, 5, and 10) in HT-Fe-MCM-41. A H2ASO4- and FeOH2? or FeOH2? (Katsoyiannis and
sample of 5 g l-1 of adsorbent in a 20-ml solution Zouboulis 2002; Mondal et al. 2007). According to
containing 3.0 mg l-1 of arsenate at pH 6 was Song et al. (2006), the reaction of arsenate with ferric at
agitated by shaker for 24 h. The remaining arsenate a low pH can form ferric arsenate (FeAsO4.2H2O).
was analyzed by HD-AAS. Figure 3 shows that the Thirdly, the effect of contact time was studied,
adsorption capacity decreased when the ferric content using 2.5 g l-1 of adsorbent. The initial arsenate
of the adsorbent was increased. This is because the concentration was 4.35 mg l-1 in 200 ml at pH 3
surface area of HT-Fe-MCM-41 decreased with (giving the highest adsorption capacity), with agita-
increases in the ferric content. In view of this, tion by shaker over a range of contact times (0–24 h).
HT-Fe-MCM-41 at the molar ratio Si/Fe 10 was The results shown in Fig. 5 reveal that the adsorption

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Environ Geochem Health (2010) 32:261–266 265

1200 1.4
Adsorption capacity (ug g )
-1

1000 1.2

1.0
800

-1
0.8

Ce qe
600 R2 = 0.99
0.6
400
0.4
200 0.2

0 0.0
0 5 10 15 20 25 0 200 400 600 800 1000 1200 1400
Time (Hour) Ce

Fig. 5 Effect of contact time on adsorption capacity of Fig. 6 Langmuir adsorption isotherm of arsenate
arsenate
Comparisons were made of the maximum adsorp-
capacity rose sharply in the first hour and then tion capacity of HT-Fe-MCM-41 for arsenate
increased more slowly during the second through with those of various other adsorbents, within a
fourth hours. After that, the adsorption capacity was similar concentration range. The adsorption capacity
in equilibrium at contact times longer than 4 h. At the of HT-Fe-MCM-41 for arsenate was the highest,
equilibrium time, the adsorption capacity was about compared, for example, to the adsorbents iron oxide-
1,000 lg g-1. Compared with adsorption materials coated cement, ferrihydrite (FH), and RH-Fe-MCM-
employed in other studies, HT-Fe-MCM-41 (Si/Fe = 41, whose capacities were reported by Kundu and Gupta
10) had an equilibrium time shorter than that of ferric (2006), Dinesh and Jr Charles (2007), and Tong-on et al.
impregnated activated carbon (Mondal et al. 2007) (2009) as 710, 250, and 278 lg g-1, respectively.
and iron oxide-loaded slag (Zhang and Itoh 2005), Our adsorbent synthesized from rice husk silica
and near to the equilibrium times of iron oxide-coated (HT-Fe-MCM-41) has advantages over other adsor-
sand (Gupta et al. 2005), iron-modified activated bents, especially in view of its higher surface area,
carbon (Chen et al. 2007), and RH-Fe-MCM-41 and adsorption capacity over a similar range of
(Tong-on et al. 2009). arsenate concentrations. In addition, the hexagonal
Finally, the effect of initial arsenate concentration structure of this adsorbent can still be maintained at
was examined. The concentrations of arsenate ranged the Si/Fe mole ratio of 10, significantly enhancing the
between 2.7 and 4.35 mg l-1 in 20 ml; 2.5 g l-1 of adsorption capacity of arsenate. Differences in arse-
adsorbent was used. The batch experiments were nate uptake with various adsorbents are associated
conducted under conditions previous studies indi- with the individual properties of each adsorbent, such
cated as optimal. It was found that the adsorption as structure, functional groups, pHZPC, and surface
capacity gradually increased as initial arsenate con- area.
centration was increased.
Within the examined concentration range of arse-
nate, the adsorption capacity was 848–1,048 lg g-1. Conclusions
The equilibrium isotherms of arsenate were described
by the Langmuir and Freundlich models. The exper- The HT-Fe-MCM-41 prepared by the hydrothermal
imental data were plotted for both the Langmuir and technique gave a higher surface area (by about 2
the Freundlich models. It was found that the adsorp- times) and crystallinity than Fe-MCM-41 prepared
tion capacity of the Langmuir isotherm, qm, was under ambient conditions. The hexagonal structure
1,111.11 lg g-1. The adsorption capacity of the was visually obvious when preparation was by the
Freundlich isotherm, KL, was 560.14 lg g-1. The hydrothermal technique. Results of batch experi-
adsorption data were well fit by the Langmuir ments showed that the arsenate adsorption capacity of
isotherm. The R2 values obtained for the Langmuir HT-Fe-MCM-41 was highest at the Si/Fe mole ratio
isotherm and for the Freundlich isotherm were about of 10. The arsenate removal rate rose sharply then
0.99 (Fig. 6) and about 0.92, respectively. was in equilibrium after 4 h. The highest adsorption

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capacity was obtained at pH 3. The adsorption Katsoyiannis, I. A., & Zouboulis, A. I. (2002). Removal of
capacity increased gradually with increases in initial arsenic from contaminated water sources by sorption onto
iron-oxide-coated polymeric materials. Water Research,
arsenate concentration. Finally, the adsorption data 36, 5141–5155.
were well fit by the Langmuir isotherm. Kundu, S., & Gupta, A. K. (2006). Arsenic adsorption onto iron
oxide-coated cement (IOCC): regression analysis of equi-
Acknowledgments Financial support was provided by the librium data with several isotherm models and their opti-
International Environmental Research Center at Gwangju mization. Chemical Engineering Journal, 122, 93–106.
Institute of Science and Technology (GIST), Republic of Mondal, P., Balomajumder, C., & Mohanty, B. (2007). A
Korea. laboratory study for the treatment of arsenic, iron and
manganese bearing ground water using Fe3? impregnated
activated carbon: effect of shaking time, pH and temper-
ature. Journal of Hazardous Materials, 144, 420–426.
References Smedley, P. L., & Kinniburgh, D. G. (2002). A review of the
source, behavior and distribution of arsenic in natural
Chen, W., Parette, R., Zou, J., Cannon, F. S., & Dempsey, B. A. waters. Applied Geochemistry, 17, 517–568.
(2007). Arsenic removal by iron-modified activated carbon. Song, S., Lopez, V. A., Hernandez, D. J., Peng, C., Monroy, M.
Water Research, 41, 1851–1858. G., & Razo, R. I. (2006). Arsenic removal from high-
Chiarakorn, S., Areerob, T., & Grisdanurak, N. (2007). Influ- arsenic water by enhanced coagulation with ferric ions
ence of functional silanes on hydrophobicity of MCM-41 and coarse calcite. Water Research, 40, 364–372.
synthesized from rice husk. Science and Technology of Sthiannopkao, S., Kim, K. W., Sotham, S., & Chop, S. (2008).
Advanced Materials, 8, 110–115. Arsenic and manganese in tube well waters of Prey Veng
Chumee, J., Grisdanurak, N., Neramittagapong, A., & and Kandal Provinces, Cambodia. Applied Geochemistry,
Witthayakun, J. (2009). Characterization of platinum-iron 23, 1086–1093.
catalyst supported on MCM-41 synthesized with rice husk Tong-on, W., Chiarakorn, S., Sthiannopkao, S., & Kim, K. W.
silica and their performance for phenol hydroxylation. (2009). Adsorption of arsenic in aqueous solution by RH-
Science and Technology of Advanced Materials, 10, Fe-MCM-41. Water Science & Technology: Water Sup-
015006. ply, 9(2), 121–126.
Dinesh, M., & Charles, U. P. Jr. (2007). Arsenic removal from Zhang, F. S., & Itoh, H. (2005). Iron oxide-loaded slag for
water/wastewater using adsorbents—a critical review. arsenic removal from aqueous system. Chemosphere, 60,
Journal of Hazardous Materials, 142, 1–53. 319–325.
Grisdanurak, N., Chairakorn, S., & Wittayakun, J. (2003). Zhang, Q., Yang, W., Wang, X., Wang, Y., Shishido, T., &
Utilization of mesoporous molecular sieves synthesized Táchira, K. (2005). Coordination structures of vanadium
from natural source rice husk silica to chlorinated volatile and iron in MCM-41 and the catalytic properties in partial
organic compounds (CVOCs) adsorption. Korean Journal oxidation of methane. Microporous and Mesoporous
of Chemical Engineering, 20(5), 950–955. Materials, 77, 223–234.
Gupta, V. K., Saini, V. K., & Jain, N. (2005). Adsorption of As
(III) from aqueous solutions by iron oxide-coated sand.
Journal of Colloid and Interface Science, 288, 55–60.

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