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CLAY-01845; No of Pages 5
Applied Clay Science xxx (2010) xxx–xxx

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / c l a y

Note

Adsorption of an anionic azo dye by chitosan/kaolin/γ-Fe2O3 composites

Hua-Yue Zhu a,b, Ru Jiang a,⁎, Ling Xiao b
a
Department of Environmental Engineering, Taizhou University, Linhai 317000, PR China
b
Key Laboratory for Biomass-Resource Chemistry and Environmental Biotechnology of Hubei Province, College of Resource and Environmental Science, Wuhan University, Wuhan 430072,
PR China

a r t i c l e i n f o a b s t r a c t

Article history: Chitosan/kaolin/nanosized γ-Fe2O3 composites were prepared by a microemulsion process and character-
Received 14 December 2009 ized by TEM, SEM and WAXRD. Many pores and pleats were visible on the surface of the composites and
Received in revised form 2 February 2010 provided a good condition for dye adsorption. Methyl orange (MO) was selected as a model anionic azo dye
Accepted 2 February 2010
to examine the adsorption behavior of the composites. Amounts of 71.0% of MO were adsorbed within
Available online xxxx
180 min from 20 mg L− 1 MO solution at pH = 6.0 by 1.0 g L− 1 adsorbent dosage. Therefore, the composites
Keywords:
can be used as a low-cost alternative for anionic dyes removal from industrial wastewater.
Kaolin © 2010 Elsevier B.V. All rights reserved.
Chitosan
γ-Fe2O3
Anionic dye
Adsorption

1. Introduction ing material of crustaceans, insects, etc. Chitosan exhibits a higher

Most of anionic dyes released during textiles, clothing, printing
and dyeing processes are considered as hazardous and toxic to some
organisms and may cause direct destruction of aquatic creatures. In
addition, dye wastewaters are commonly characterized by high salt
content and a low biodegradation potential (Alinsafi et al., 2005),
which makes effective removal by conventional wastewater treat-
ment processes difficult (Vimonses et al., 2009).
One of the most effective methods for removal of organic dye
pollutant is by adsorption (Crini and Badot, 2008). In recent years,
many studies have focused on seeking cheap, locally available and
effective adsorbents, such as waste biopolymers (Crini and Badot,
2008; Cheung et al., 2009), clays and clay minerals (Gecol et al., 2006;
Karim et al., 2009; Tang et al., 2009; Vimonses et al., 2009), etc. Among
these materials, raw kaolin and chitosan are relatively cheap and
exhibit higher adsorption capacities (Crini and Badot, 2008; Tang
et al., 2009). Kaolin is one of the well-known low-cost raw clays due to
its good adsorption properties (Vimonses et al., 2009). However,
kaolin has little affinity to anionic species. For the above reason, the
surface of kaolin must be modified to incorporate positively charged
sites prior to anion adsorption attempts (Gecol et al., 2006). Chitosan
is a cationic biopolymer obtained from alkaline N-deacetylation of
chitin, the second most abundant biopolymer in nature and support-
adsorption capacity and faster adsorption rate of anionic dye
pollutants than many conventional adsorbents due to the presence
of large amounts of amino (–NH2) and hydroxyl (–OH) groups (Jiang
et al., 2009;Zhu et al., 2009). In acidic solution, the amino groups of
chitosan are easily protonated and bounded anionic dye anions (Crini
and Badot, 2008). Thus, various chitosan-based composites, especially
chitosan–clay mineral composites have been tested as adsorbents for
dyes and metal ions (Chatterjee et al., 2009;Pathavuth and Punnama,
2009; Wang et al., 2009). In addition, composite nanoparticles as
adsorbents are drawing more and more attention due to their high
specific surface area, chemical and mechanical stability, and a variety
of surface and structural properties (Murray, 2000; Liu and Zhang,
2007). Nanoparticles embedded in porous polymer materials can
expand the adsorption capacity due to enhanced electrostatic
interaction (Luo and Zhang, 2009). However, to our knowledge,
there is very little information about chitosan entrapping kaolin and
nanosized γ-Fe2O3 as adsorbent of anionic dyes.
In the present study, chitosan/kaolin/nanosized γ-Fe2O3 compo-
sites were prepared by microemulsion process and characterized by
SEM, TEM and WAXRD. Methyl orange (MO) was selected as a model
dye to examine the adsorptive potential of chitosan/kaolin/γ-Fe2O3
composites towards anionic dyes.
2. Experimental

⁎ Corresponding author. Postal address: No. 605, Orient Avenue, Linhai City (317000),
Zhejiang Province, PR China. Tel.: +86 1586 7636 396; fax: +86 0576 8513 7066.
E-mail addresses: zhuhuayue@126.com (H.-Y. Zhu), jiangru0576@163.com
(R. Jiang), xiaoling9119@yahoo.cn (L. Xiao).
2.1. Materials
Commercial-grade kaolin was obtained from Zhejiang Songyang
Kaolin Ltd. (Lishui, China). Chitosan with 91.7% deacetylation was

0169-1317/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2010.02.003

Please cite this article as: Zhu, H.-Y., et al., Adsorption of an anionic azo dye by chitosan/kaolin/γ-Fe2O3 composites, Appl. Clay Sci. (2010),
doi:10.1016/j.clay.2010.02.003
 ARTICLE IN PRESS
2 H.-Y. Zhu et al. / Applied Clay Science xxx (2010) xxx–xxx
provided by Yuhuan Jinke Biochemisty Industry Co., Ltd. (Taizhou,
China) and used without any further purification. γ-Fe2O3 nanopar-
ticles (about 30 nm outer diameter and 98% of purity) were purchased
from Tongrenweiye Technology Co., Ltd. (Shijiazhuang, China).
Methyl orange supplied by Zhejiang Yongjia Fine Chemical Factory
(Wenzhou, China) was used as a model anionic dye. Other chemicals
used were of analytical grade. All solutions were prepared using
twice-distilled water.
2.2. Preparation of chitosan/kaolin/γ-Fe2O3 composites
2 g chitosan were dissolved in 100 mL 2% (v/v) of acetic acid
solution under ultrasonic stirring. Then 0.4 g maghemite (γ-Fe2O3)
nanoparticles and 0.4 g kaolin were added under stirring for 1 h.
150 mL OP emulsifier and 20 mL Span-80 were added during stirring
at 400 rpm. Subsequently, 2 mL 25% (v/v) glutaraldehyde as cross-
linking agent was added dropwise. The emulsion was kept in a water
bath at 40 °C for 1 h. 1 mol L− 1 NaOH was used to adjust pH to 9–10.
Finally, the product was washed with N, N-dimethylformamide,
ethanol and twice-distilled water for 3–4 times, respectively, and
dried under atmospheric condition.
2.3. Characterization
Transmission electron microscopy (TEM) observation of samples
was carried out on a JEM 2010 electron microscope (Tokyo, Japan).
Morphological features and surface characteristics of samples were
obtained from scanning electron microscopy (SEM) using a Hitachi
Fig. 1. TEM image of γ-Fe2O3 nanoparticles (a) and typical SEM images of kaolin (b) and BKF composites (c,d).
Please cite this article as: Zhu, H.-Y., et al., Adsorption of an anionic azo dye by chitosan/kaolin/γ-Fe2O3 composites, Appl. Clay Sci. (2010),
doi:10.1016/j.clay.2010.02.003
SX-650 scanning electron microscope (Tokyo, Japan). Wide-angle X-
ray diffraction (WAXRD) measurement was performed on a D8-
Advance XRD diffractometer (Bruker, German) at a scan rate of 4°
2θ min− 1 from 5° to 65° with Cu Kα target.
2.4. Batch adsorption experiments
Standard solutions of desired concentrations were prepared by
diluting 1.0 g L− 1 stock solution of MO. Batch adsorption experiments
were carried out using a KYC-1102C thermostatic rotary shaker
(Ningbo Jiangnan Instrument Factory, China). For a typical adsorption
experiment, 1.0 g L− 1 adsorbent was dispersed in 50 mL of 20 mg L− 1
aqueous MO solution without adjusting pH. The dispersion was
stirred at an agitation speed of 100 rpm at 37 ± 0.2 °C. At given time
intervals, 4 mL of the dispersions was collected and filtered. The dye
concentrations were determined by measuring the absorbance at the
maximum absorption of MO (464.9 nm) using a Cary 50 UV–Vis
spectrophotometer (Varian, USA).
The effect of pH on adsorption capacities was determined in the pH
range from 2.93 to 11.38. pH was adjusted with 0.1 mol L− 1 NaOH or
0.1 mol L− 1 HCl and measured by a Model 990 pH/conductivity meter
(Jiangsu Electroanalytical Instrument Factory, China). Different
amounts of adsorbent in the range of 0.2–1.4 g L− 1 were used to
examine the effect of adsorbent dosage on adsorption of MO. The
effect of competitive anions was investigated by adding 0.01 mol L− 1
corresponding sodium salt (NaCl, NaNO3, Na2SO4, Na2CO3 and
Na3PO4) into the adsorption system.
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3. Results and discussion
3.1. Characterization of adsorbents
The diameter of γ-Fe2O3 was in the range of 17–40 nm (Fig. 1a).
Fig. 1b,d shows the surface morphology of kaolin and the composites.
Kaolin presented particles of 2–10 μm (Fig. 1b). The diameter of the
composite particles was in the range from 100 to 330 μm (Fig. 1c). The
surface of the composite particles was rough and occupied by
nanosized γ-Fe2O3 and kaolin particles. Many pores and pleats were
present on the surface, providing a good possibility for dyes to be
trapped and adsorbed.
The main reflections of kaolinite (Fig. 2a) were at 2θ = 12.36°,
19.94°, 24.90°, 35.98°, 38.46°, 45.66°, 55.12° and 62.34° matching the
JCPDS database file (PDF-01-089-6538) (Nandi et al., 2008; Nandi
et al., 2009b). The XRD pattern of chitosan (Fig. 2b) exhibited
characteristic reflections at 2θ = 9.82° and 19.88°, which coincided
with the main reflections of the pattern of “tendon hydrate
polymorph” in chitosan reported previously (Hu et al., 2007). Six
distinctive reflections of γ-Fe2O3 were found at 2θ of 30.36°, 35.64°,
43.36°, 53.84°, 57.34° and 62.98° corresponding to the (220), (311),
(400), (422), (511) and (440) lattice planes of maghemite (Fig. 2c)
(JCPDS No.39-1346) (Jing, 2006; Cao et al., 2009). In the XRD pattern
of the composites (Fig. 2d), reflections at 2θ of 29.88°, 35.48°, 54.08°,
57.94° and 64.00° corresponded to the (220), (311), (422), (511) and
(440) lattice planes of maghemite. The reflection at 2θ of 43.36° was
absent. In addition, the main reflections of ideal kaolinite at 2θ of
12.38°, 24.90°, 35.48°, 38.54°, 45.50° and 62.36° could be found and
reflections at 2θ of 19.94° and 55.12° disappeared. A series of new
reflections appeared at 14.80°, 18.92°, 33.46°, 41.1° and 49.22°.
Fig. 2. WAXRD patterns of raw kaolin (a), chitosan (b), nanosized γ-Fe2O3 (c) and BKF composites (d).
Please cite this article as: Zhu, H.-Y., et al., Adsorption of an anionic azo dye by chitosan/kaolin/γ-Fe2O3 composites, Appl. Clay Sci. (2010),
doi:10.1016/j.clay.2010.02.003
3
3.2. Adsorption studies
3.2.1. Effect of adsorbent dosage
Adsorbent dosage is an essential parameter which must be
carefully adjusted during wastewater treatment. The effect of
adsorbent dosage (varying from 0.2 g L− 1 to 1.4 g L− 1) on MO dye
removal is presented in Fig. 3. Initially, a rapid increase of adsorption
with the increasing adsorbent dosage was attributed to availability of
more adsorption sites (Almeida et al., 2009). A further increase of the
adsorbent dosage from 1.0 g L− 1 to 1.4 g L− 1 didn't much increase
dye removal (only from 75.8% to 81.9%). The amount adsorbed (qe)
decreased from 34.9 mg g− 1 to 11.6 mg g− 1 when the adsorbent
dosage was increased from 0.2 g L− 1 to 1.4 g L− 1. The decrease of
adsorption was due to the concentration gradient between adsorbent
and adsorptive (Nandi et al., 2009a).
3.2.2. Effect of pH
The effect of initial solution pH on MO adsorption is shown in
Fig. 4. The maximum dye removal was 82.3% at pH 2.9 followed by a
slight decrease from pH 2.9 to 7.1. MO removal then decreased
significantly at pH N 7.1. Quinoid form of MO occurs at low pH value
and rearranges in azo structure at high pH (Ma et al., 2007).
The decrease of dye adsorption with increasing pH can be explained
by the electrostatic interaction between the adsorbent surface and the
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Fig. 3. Effect of adsorbent dosage on MO removal (initial MO concentration: 20 mg L− 1,
natural pH, agitation speed: 100 rpm, temperature: 37 °C).
dye anions. On the one hand, because pKa of chitosan is around 6.20,
below pH 5 almost 90% of active sites were protonated, while at pH 4
more than 99% (Graciela, et al., 2005). On the other hand, at pH values
lower than the p.z.c of a mineral, the surface had a net positive charge
and tended to accumulate anionic species (Lagaly, 2006) According to
Nandi's research, p.z.c. of kaolin was reached at pH 7.0 (Nandi et al.,
2009a,b). Therefore, the dye anions can be bound by electrostatic
attractions to both chitosan and kaolinite when the ambient pH was
lower than 7.1. Additionally, the abundant presence of OH− ions in basic
solution was competitive with the dye anions (Vimonses et al., 2009).
3.2.3. Effect of competitive anions
Various electrolytes are added to dyeing bath in textile industries
to improve color fastness (Riga et al., 2007). Therefore, the effect of
competitive anions on dye adsorption cannot be neglected. Compe-
titive anions are expected to interfere in the adsorption process and
there was a direct correlation between competitive anions and the
amount of dye anions adsorbed (Ni et al., 2007). The effect of Cl−,
NO− 2−
3 , SO4 , CO3
2−
and PO3−4 was studied by adding 0.01 mol L− 1
sodium salt (NaCl, NaNO3, Na2SO4, Na2CO3 and Na3PO4) to 20 mg L− 1
MO without pH adjusting, 1.0 g L− 1 adsorbent dosage and 100 rpm
Fig. 4. Effect of initial solution pH on MO removal (initial MO concentration: 20 mg L− 1,
adsorbent dosage: 1.0 g L− 1, agitation speed: 100 rpm, adsorption time: 500 min,
temperature: 37 °C).
Please cite this article as: Zhu, H.-Y., et al., Adsorption of an anionic azo dye by chitosan/kaolin/γ-Fe2O3 composites, Appl. Clay Sci. (2010),
doi:10.1016/j.clay.2010.02.003
Fig. 5. Effect of competitive anions on MO removal (initial MO concentration: 20 mg L−1,
adsorbent dosage: 1.0 g L−1, natural pH, agitation speed: 100 rpm, temperature: 37 °C).
agitation speed. The result is shown in Fig. 5. The order of decolorization
was: no addition ≫ Cl− N NO− 2− 2− 3−
3 N SO4 ≫ CO3 N PO4 , indicating that
addition of competitive anions decreased dye adsorption. In the pres-
ence of 0.01 mol L− 1 PO3−
4 , almost no adsorption of MO was observed.
Competition of the anions is often explained by their preferred strong
adsorption. The multivalent charge of phosphate anions could be
strongly bound by chitosan/kaolin/γ-Fe2O3 composites.
4. Conclusions
Kaolin and γ-Fe2O3 nanoparticles were entrapped in chitosan
beads by a microemulsion process. Many pores and pleats on the
surface of the composite particles provided a good condition for dye
adsorption. 71.0% of MO could be removed within 180 min of
adsorption from a 20 mg L− 1 MO solution at pH = 6.0 by 1.0 g L− 1
composites. The results will be useful for future up-scaling using the
novel materials as a low-cost adsorbent for removal of anionic azo
dyes.
Acknowledgements
The authors wish to acknowledge the financial support of the
research by Specialized Research Fund for the Bairen Doctor Program
of Taizhou University (No. TZUDF 2007-167). The authors also want to
thank Center of Electron Microscopy in Wuhan University for
assistance with the characterization of samples.
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