Professional Documents
Culture Documents
com
State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering,
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, China
Received 22 August 2007; received in revised form 9 October 2007; accepted 11 October 2007
Available online 18 October 2007
Abstract
The halloysite nanotubes (HNTs) were used as nano-adsorbents for the removal of the cationic dye, methylene blue (MB), from aque-
ous solutions. The dye adsorption experiments were carried out by using bath procedure. Experimental results have shown that the basic
pH, increasing initial dye concentration and lower temperature favored the adsorption. The dye adsorption equilibrium was rapidly
attained after 30 min of contact time. The factors controlling the adsorption process were also calculated and discussed. And a maximum
adsorption capacity of 84.32 mg/g of methylene blue was achieved. It was noted that the dye adsorbed halloysite nanotubes had poor
stability in aqueous suspension and deposited completely within 30 min while the original aqueous suspension of halloysite nanotubes
remained stable for months.
Ó 2007 Elsevier Inc. All rights reserved.
1387-1811/$ - see front matter Ó 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.10.018
420 M. Zhao, P. Liu / Microporous and Mesoporous Materials 112 (2008) 419–424
natural deposits in countries such as China, America, Bra- 319.86; maximum wavelength: 662 nm) supplied by
zil, France and so on. It possesses a regular nanotubular Merck, was not purified prior to use.
morphology, bulk structure and rich mesopores and
nanopores [32,33]. Recently, it was used as adsorbents 2.2. Methylene blue absorption
[34] and nanotemplates or nanoscale reaction vessels
instead of carbon nanotubes or boron nitride nanotubes All of the methylene blue solution was prepared with
[35–37]. distilled water. The pH of the solution was adjusted with
In the present study, halloysite nanotubes (HNTs) were 0.1 N HCl or 0.1 N NaOH by using a Model 3C Digital
used as adsorbents for the removal of cationic dye from an pH-meter with a combined pH electrode. The pH-meter
aqueous solution. Methylene blue was selected as a model was standardized with NBS buffers before every
compound in order to evaluate the capacity of HNTs for measurement.
the removal of dyes from aqueous solutions. The aim of The effect of contact time on the amount of dye
this study was to investigate the adsorption of methylene adsorbed was investigated at 159.93 mg/l (0.50 m mol/l)
blue onto HNTs, which is a low-cost adsorbent for the initial concentration of dye and at different temperatures
removal of dyes. (20, 45 and 70 °C). Fifteen milliliter HNTs suspension
(including 0.235 g HNTs) was mixed with 85 ml MB dye
2. Experimental and methods solution.
For the other adsorption experiments, 15 ml HNTs sus-
2.1. Raw materials pension (including 0.235 g HNTs) was added into 85 ml of
dye solution with known initial concentration at desired
Halloysite clay was obtained from Hebei Province, pH and temperature and stirred with a rate of 150 rpm
China. It was pretreated by the followed procedure: for 180 min. A constant bath was used to keep the temper-
250 g raw halloysite clay and 500 ml water were mixed ature constant. At the end of the adsorption period, the
and milled with SF400 type wit sand-grinding dispersing solution was centrifuged for 10 min at 15,000 rpm. After
machine at 4000 rpm for 2 h. The halloysite nanotubes centrifugation, the dye concentration in the supernatant
(HNTs) suspension was centrifugated (3000 rpm for solution was analyzed using a UV spectrophotometer
3 min) to throw away the deposit. The stable suspension (Shimadzu UV-260) by monitoring the absorbance
was used for further experiments. Its TEM image was changes at a wavelength of maximum absorbance
shown in Fig. 1 (The morphology of the HNTs was char- (662 nm). The samples were pipetted from the medium
acterized with a JEM-1200 EX/S transmission electron reaction by the aid of a very thin point micropipette,
microscope (TEM). The bare HNTs suspended colloid which prevented the transition to the solution of the
solution and was deposited on a copper grid covered with HNTs samples. Preliminary experiments showed that the
a perforated carbon film). Methylene blue (MB) (CI: effect of the separation time on the amount of adsorbed
52015; chemical formula: C16H18ClN3S; molecular weight: dye was negligible.
The amounts of dye adsorbed on HNTs at any time, t,
were calculated from the concentrations in solutions before
and after adsorption. At any times, the amount of MB
adsorbed (mol/g) (qt), onto HNTs was calculated from
the mass balance equation as follows:
qt ¼ V ðC 0 –C e Þ=W ð1Þ
qt (mg/g)
65.2
investigated as a function of initial dye concentration. The
64.8
effect of initial dye concentration and contact time on the
removal rate of MB by HNTs is shown in Fig. 2. As shown, 64.4
the adsorption increases with increasing initial dye concen- 64.0
tration. The results show that dye uptake is rapid for the 63.6
first 15 min and finally attains saturation within about
63.2
30 min. The equilibrium was attained at 30 min.
0 30 60 90 120 150 180
The amount of MB adsorbed at equilibrium increases
t (min)
from 0.1276 to 0.2588 m mol/g (40.81–82.78 mg/g) by
increasing the initial MB concentration from 0.30 to Fig. 3. Effect of contact time and initial pH on the removal rate of MB
0.70 m mol/l with the adsorption condition of initial pH onto HNTs from aqueous solutions (20 °C, C0: 159.93 mg/l).
7 and 20 °C. It is near to the sepiolite and much higher than
those other clay minerals [28]. that the adsorption equilibrium was attained faster with the
higher initial pH condition.
3.1.2. Effect of pH
Effect of pH on the removal rate of MB by HNTs is 3.1.3. Effect of temperature
shown in Fig. 3. As the pH increased, the removal rate Fig. 4 exhibits contact time versus adsorbed amount
increased. The pH value of the dye solution plays an graph at different temperatures. The initial pH was selected
important role in the whole adsorption process and partic- as 7 in order to avoid the impossible breakage of HNTs at
ularly on the adsorption capacity. The zeta-potential higher temperatures because SiO2 is the main component.
behavior of halloysite nanotubes is mostly negative at pH The equilibrium adsorption capacity of MB onto HNTs
2–12 due to the surface potential of SiO2 with a small con- was found to decrease with increasing temperature, decreas-
tribution from the positive Al2O3 inner surface [36,39,40] ing from 0.2081 m mol/g at 20 °C to 0.2058 m mol/g at 70 °C
(the chemical properties on the halloysite nanotubes outer- indicating that the dye adsorption on the adsorbent was
most surface are similar to the properties of SiO2 while the favored at lower temperatures. And the adsorption equilib-
properties of the inner cylinder core could be associated rium was attained slowly with the higher temperature.
with Al2O3). And it exhibits a strongly pH-dependent sur-
face charge. With the increasing of pH, the surface of 3.2. Adsorption kinetics
HNTs becomes more negatively charged, thereby increas-
ing electrostatic attractions between positively charged 3.2.1. The pseudo-first-order kinetic model
dye anions and negatively charged adsorption sites and The pseudo-first-order kinetic model has been widely
causing an increase in the dye adsorption. It was also found used to predict dye adsorption kinetics. A linear form of
pseudo-first-order model was described by Lagergren [41]:
90
66.9
84
78 66.6
72 66.3
66
qt (mg/g)
66.0
qt (mg/g)
60
95.96mg/L
65.7
54 159.93mg/L
223.90mg/L 65.4
48 o
20 C
42 65.1
o
45 C
o
36 70 C
64.8
30
0 30 60 90 120 150 180 0 30 60 90 120 150 180
t (min ) t (min)
Fig. 2. Effect of contact time and initial dye concentration on adsorption Fig. 4. Effect of contact time and temperature on the removal rate of MB
of MB onto HNTs from aqueous solutions (20 °C, pH 7). onto HNTs from aqueous solutions (C0: 159.93 mg/l, pH 7).
422 M. Zhao, P. Liu / Microporous and Mesoporous Materials 112 (2008) 419–424
Table 1
Adsorption kinetic parameters of methylene blue onto HNTs 66.6
Pseudo-first-order T (°C)
66.3
20 45 70
kpf, min1 0.011 0.023 0.017 66.0
qeb, mg/g 66.55 66.46 65.82
r21 0.7912 0.8753 0.9976
q t (mg/g)
65.7
Pseudo-second-order C0 (mg/l)
95.96 159.93 223.90 65.4 o
20 C
qea, mg/g 40.82 66.53 84.32 o
45 C
kps, g/mg min 3.97 0.195 0.019 o
qeb, mg/g 40.82 66.55 86.35 65.1 70 C
References
[31] J.H. Huang, Y.F. Liu, Q.Z. Jin, X.G. Wang, J. Yang, J. Hazard. [38] M. Dogan, M. Alkan, Chemosphere 50 (2003) 517–528.
Mater. 143 (2007) 541–548. [39] G. Tari, I. Bobos, C.S. Gomes, J.M. Ferreira, J. Colloid Interf. Sci.
[32] S.R. Levis, P.B. Deasy, Int. J. Pharm. 243 (2002) 125–134. 210 (1999) 360–366.
[33] X.C. Liu, X.Y. Chuan, A.P. Wang, F.Y. Kang, Acta Geologica [40] S. Baral, S. Brandow, B.P. Gaber, Chem. Mater. 6 (1994) 1227–1232.
Sinica 80 (2006) 278–284. [41] V.C. Taty-Costodes, H. Fauduet, C. Porte, A. Delacroixs, J. Hazard
[34] M.T. Viseras, C. Aguzzi, P. Cerezo, C. Viseras, C. Valenzuela, Mater. 105 (2003) 121–142.
Micropor. Mesopor. Mater., in press, doi:10.1016/j.micromeso. [42] V. Vadivelan, K.V. Kumar, J. Colloids. Interf. Sci. 286 (2005) 90–100.
2007.03.033. [43] M. Dogan, M. Alkan, A. Turkyılmaz, Y. Ozdemir, J. Hazard Mater.
[35] S.J. Antill, Aust. J. Chem. 56 (2003) 723. B 109 (2004) 141–148.
[36] D.G. Shchukin, G.B. Sukhorukov, R.R. Price, Y.M. Lvov, Small 1
(2005) 510–513.
[37] A.P. Wang, F.Y. Kang, Z.H. Huang, Z.C. Guo, X.Y. Chuan,
Micropor. Mesopor. Mater., in press, doi:10.1016/j.micromeso.
2007.04.021.