Journal of Colloid and Interface Science 272 (2004) 399403 www.elsevier.

com/locate/jcis

Removal of uoride from water through ion exchange by mesoporous Ti oxohydroxide

Li Ngee Ho, Tatsumi Ishihara, Soichiro Ueshima, Hiroyasu Nishiguchi, and Yusaku Takita
Department of Applied Chemistry, 870-1192 Oita University, Oita, Japan Received 30 June 2003; accepted 19 August 2003

Abstract In our previous study, we found that Ti(OH)4 exhibited uoride ion exchange properties. In order to improve the ion exchange capacity, mesoporous Ti oxohydroxide (TiOx (OH)y ) had been prepared by using dodecylamine as template. Zirconia and silica had been introduced into the mesoporous Ti oxohydroxide to enhance the ion exchange capacity. The mesoporous structure and the morphology of the mesoporous materials obtained were conrmed using XRD and SEM, respectively. A uoride ion exchange study was done on each sample. Results showed that mesoporous Ti oxohydroxide containing zirconia exhibited the highest uoride ion exchange capacity, as it has the smallest particle size, with high uniformity among the mesoporous materials prepared. 2003 Elsevier Inc. All rights reserved.
Keywords: Fluoride; Titanium oxohydroxide; Zirconia; Silica; Ion exchange; Pollution

1. Introduction Fluoride-related health hazards are considered to be a major environmental problem in many regions of the world [1]. The presence of uoride in drinking water can be benecial or detrimental depending on the concentration [2]. According to WHO standards, the acceptable limit of uoride in potable water is 1.5 mg/l [3]. Excess uoride consumption causes dental and skeletal uorosis problems. Increasing public concern regarding excessive uoride content in drinking water has led to stringent environmental regulations on the levels of uoride in water supplies. Consequently, treatment of uoride has become a worldwide important subject nowadays. Fluoride waste can be found in the wastewater derived from industries such as semiconductors, metal processing, fertilizers, and glass manufacture [4]. Many methods have been developed to remove excessive uoride from water, namely, adsorption, ion exchange, precipitation, electrolysis, Donnan dialysis, and electrodialysis [5]. Among these methods, precipitation and adsorption or ion exchange are the most common and economical methods used. In the precipitation method, chemicals such
* Corresponding author.

E-mail address: holingee@cc.oita-u.ac.jp (L.N. Ho). 0021-9797/$ see front matter 2003 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2003.08.051

as lime (Ca(OH)2), dolomite (magnesium salts), and alum (Al2 (SO4 )3 ) have been widely used [6]. Although the precipitation method is simple and economical, the required dosages are very high, which causes sludge disposal problems. Adsorbents such as alumina [7], y ash [8], and carbon [9] are used to adsorb uoride from wastewater. However, the adsorption capacities of these methods decrease sharply under saline conditions [10]. On the other hand, it was reported that CeO2 is able to exchange uoride ions selectively [11]. CeO2 dispersed into polymer matrix is a commercial uoride ion exchanger (Read-F, Asahi Kasei Co. Ltd.) [12]. However, it is expensive in term of cost. Therefore, development of a non-noxious uoride ion exchanger with excellent ion exchange capacity and reasonable price is strongly needed. As discussed in our previous study [12], Ti(OH)4 prepared by precipitation from TiOSO4 exhibited uoride ion exchange properties. In order to improve the ion exchange capacity, Ti(OH)4 has been prepared by solgel hydrolysis using titanium isopropoxide. Besides, mesoporous Ti oxohydroxide had been prepared by using dodecylamine as template. This is due to the porous structures, which are such that they allow molecules access to vast internal surfaces and cavities which can enhance the adsorptive capacity of these porous solids [13].

400

L.N. Ho et al. / Journal of Colloid and Interface Science 272 (2004) 399403

2. Materials and methods 2.1. Preparation of Ti(OH)4 by hydrolysis solgel method Titanium isopropoxide, 5.0 g (Wako, 95%) and 5.0 ml of 1 mol/l H2 SO4 (Wako) were added into 25 ml of 2-propanol (Wako, 99.5%) drop-wise. The mixture was aged for 24 h at room temperature, 28 C, followed by drying at room temperature. 2.2. Preparation of Ti(OH)4 by precipitation method Titanium hydroxide was prepared by precipitation in aqueous TiO(SO4 ) solution by the addition of aqueous ammonia solution. The precipitates were then washed until pH ca. 7 before dried in an oven at 343 K for 12 h. 2.3. Synthesis of mesoporous Ti oxohydroxide A 2:1 mole ratio of titanium isopropoxide (5.0 g) and dodecylamine (1.63 g) (Wako, 95%) was added into D.I. water (25 ml) in drop-wise, followed by 0.1 mol/l HCl (1.0 ml) (Wako). The mixture was allowed to stand for aging for 24 h at 40 C before put into the oven to dry at 60 C. 2.4. Synthesis of mesoporous TiOx (OH)y containing zirconia and mesoporous TiOx (OH)y containing silica The procedure are same as in the synthesis of mesoporous Ti oxohydroxide except with the addition of zirconium n-propoxide (Kishida Chemical, 70% in 1-propanol) in the preparation of mesoporous TiOx (OH)y containing zirconia (Ti:Zr mol ratio 9:1) and the addition of tetraethyl orthosilicate (Wako, 95%) in the synthesis of mesoporous TiOx (OH)y containing silica (Ti:Si mol ratio 9:1). 2.5. Characterization As proposed by Soler-Illia and Sanchez in the modulation of hybrid interface (MHI) mechanism [14], high quantities of water encourage a rapid condensation process, which leads to the formation of hydrophilic oxo oligomers. In the presence of HCl, condensates of general formula TiXx (OH)y O2(x +y)2 (XOR or Cl, x 0.30.7, and y 00.2) are obtained [15]. The co-condensation of the hydrophilic clusters around the micelles leads to the formation of the inorganic network. The overall hydrophilic conditions assist polymer folding, the hydrophilic Ti oxohydroxo species and the alkyl surfactants (dodecylamine) match together at the hybrid interface, creating a condition for segregation at the mesoscale [15]. All the mesoporous materials prepared above were analyzed with XRD (Rigaku) in powder form. Fig. 1 shows the XRD patterns of mesoporous TiOx (OH)y , mesoporous TiOx (OH)y containing zirconia, and mesoporous TiOx

Fig. 1. XRD pattern of mesoporous TiOx (OH)y , mesoporous TiOx (OH)y containing zirconia, mesoporous TiOx (OH)y containing silica.

(OH)y containing silica. A single broad peak can be observed at 3 where d = 39.76, 36.18, and 34.22 , respectively, conrming that the porous structures had been formed. 2.6. Ion exchange study Ion exchange study had been done on each obtained Ti(OH)4 and mesoporous Ti oxohydroxide 500 ml of 50 ppm uoride at pH 5 were prepared by mixing 0.0552 g of sodium uoride with 4.1057 g of sodium acetate and 1.65 ml of acetic acid. Then 1.00 g of ion exchanger was added into the solution and stirred for 8 h. The uoride concentration was monitored using a uoride selective electrode (Horiba, #6561-10C).

3. Results and discussion 3.1. Ion exchange kinetics of uoride ions on ion exchangers in different concentrations Figs. 2, 3, and 4 depict the ion exchange kinetics of uoride on Ti(OH)4 obtained from the precipitation method,

Fig. 2. Ion exchange kinetics of uoride ions on Ti(OH)4 obtained from precipitation method at different ion exchanger concentrations.

L.N. Ho et al. / Journal of Colloid and Interface Science 272 (2004) 399403

401

Fig. 3. Ion exchange kinetics of uoride ions on Ti(OH)4 obtained from hydrolysis solgel method at different ion exchanger concentrations. Fig. 5. Ion exchange kinetics of uoride ions on mesoporous TiOx (OH)y and Ti(OH)4 obtained from precipitation and solgel method, respectively.

Fig. 4. Ion exchange kinetics of uoride ions on mesoporous TiOx (OH)y at different ion exchanger concentrations.

Ti(OH)4 obtained from the hydrolysis solgel method, and mesoporous Ti oxohydroxide, respectively. Different ion exchanger concentrations were performed at pH 5 and a uoride concentration of 50 ppm. 3.2. Ion exchange kinetics of uoride ions on Ti(OH)4 and mesoporous Ti oxohydroxide Fig. 5 shows the ion exchange kinetics of uoride ions on Ti(OH)4 and mesoporous Ti oxohydroxide. Compared with the Ti(OH)4 obtained from TiOSO4 precipitation, ion exchange capacity was signicantly improved on the mesoporous Ti oxohydroxide and Ti(OH)4 obtained from the hydrolysis solgel method. It was found that mesoporous Ti oxohydroxide exhibited the greatest ion exchange capacity among all the samples. Besides, the ion exchange capacity of Ti(OH)4 obtained from the hydrolysis method at room temperature is slightly lower than that of mesoporous Ti oxohydroxide. This is due to the bulkiness of the Ti(OH)4 particle, which reduce the diffusion efciency of the uoride ions into the particle to exchange with the hydroxyl group. However, in the case of the mesoporous Ti oxohydroxide, high ion exchange capacity is attributable to the
Fig. 6. TEM image of the mesoporous TiOx (OH)y .

porous structures of the materials, which render them accessible to the uoride ions easily. Fig. 6 shows the TEM image of the mesoporous Ti oxohydroxide, which reveals wormholelike motifs in which there is no apparent long-range pore order. Despite this, these materials appear to possess relatively uniform channel spacing [16]. 3.3. Comparison of ion exchange kinetics of uoride ions on mesoporous TiOx (OH)y , mesoporous TiOx (OH)y containing silica, and mesoporous TiOx (OH)y containing zirconia In order to enhance the ion exchange capacity, zirconia and silica have been introduced into mesoporous TiOx (OH)y . Referring to Fig. 7, the ion exchange capacity was obviously increased after silica and zirconia were intro-

402

L.N. Ho et al. / Journal of Colloid and Interface Science 272 (2004) 399403

(a) Fig. 7. Ion exchange kinetics of uoride on mesoporous TiOx (OH)y , mesoporous TiOx (OH)y containing silica, and mesoporous TiOx (OH)y containing zirconia.

duced into the mesoporous Ti oxohydroxide structure. The ion exchange capacity of these three mesoporous materials increase in the following order: mesoporous TiOx (OH)y < mesoporous TiOx (OH)y containing zirconia < mesoporous TiOx (OH)y containing zirconia. It was found that mesoporous TiOx (OH)y containing zirconia showed the greatest ion exchange capacity. This can be explained by the surface structures of the materials, as shown in the following SEM pictures (Figs. 8a8c). Referring to Fig. 8c, small cubic-like crystal 0.3 to 1 m in size form large spherical aggregates of 2 to 5 m. The particles are quite small and uniform, unlike the case of mesoporous TiOx (OH)y (Fig. 8a), where the particle sizes range from 1.5 to 8 m. Smaller and more even particles in mesoporous TiOx (OH)y containing zirconia lead to a relatively higher external surface-area-to-volume ratio and reduce mass transfer resistance [17]. The uniform particles along with the large internal surface area of these materials enable them accessible to the uoride ions and more uoride ions can exchange with the hydroxyl groups on the surface of the materials. Hence, increase the ion exchange capacity. However, vice versa in the case of mesoporous TiOx (OH)y . Therefore, the particle size of the mesoporous materials increase in the order of: mesoporous TiOx (OH)y containing zirconia < mesoporous TiOx (OH)y containing silica < mesoporous TiOx (OH)y which is just opposite to the order of the ion exchange capacity for the mesoporous materials as mentioned above.

(b)

(c) Fig. 8. SEM pictures of (a) mesoporous TiOx (OH)y , (b) mesoporous TiOx (OH)y containing silica, and (c) mesoporous TiOx (OH)y containing zirconia.

4. Summary In this study, we can conclude that (i) Ion exchange capacity was signicantly improved on mesoporous TiOx (OH)y and Ti(OH)4 obtained from hydrolysis solgel method.

(ii) Ion exchange capacity of Ti(OH)4 obtained from hydrolysis solgel method is slightly lower than mesoporous TiOx (OH)y as the latter possess porous structures which enable uoride ions access easily to ion exchange with the hydroxyl groups.

L.N. Ho et al. / Journal of Colloid and Interface Science 272 (2004) 399403

403

(iii) Ion exchange capacity increased in the following order: mesoporous TiOx (OH)y < mesoporous TiOx (OH)y containing silica < mesoporous TiOx (OH)y containing zirconia. (iv) Adversely, the particle size of the materials decreased in the order mesoporous TiOx (OH)y > mesoporous TiOx (OH)y containing silica > mesoporous TiOx (OH)y containing zirconia.

References
[1] D. Prakasini Das, J. Das, K. Parida, J. Colloid Interface Sci. 261 (2003) 213220. [2] A.M. Raichur, M. Jyoti Basu, Sep. Purif. Technol. 24 (2001) 121127. [3] R. Helmer, Environmentalist 19 (1999) 11. [4] F. Shen, X. Chen, P. Gao, G. Chen, Chem. Eng. Sci. 58 (2003) 987 993.

[5] Y. Cenggeloglu, E. Kir, M. Ersoz, Sep. Purif. Technol. 28 (2002) 81 86. [6] C.-L. Yang, R. Dluhy, J. Haz. Mater. B 94 (2002) 239252. [7] B.S.N. Murty, V. Ravi, P.J. Reddy, R.C. Reddy, Pollut. Res. 16 (3) (1997) 177182. [8] A.K. Chaturvedi, K.P. Yadav, K.C. Pathak, V.N. Singh, Air Soil Pollut. 49 (1990) 5161. [9] R. Peikos, S. Paslawska, Fluoride 32 (1999) 1419. [10] A. Sivasamy, K.P. Singh, D. Mohan, M. Maruthamuthu, J. Chem. Technol. Biotechnol. 76 (2001) 717772. [11] J. Nomura, H. Imai, T. Miyake, ACS Sympos. Ser. 442 (1990) 152 172. [12] T. Ishihara, Y. Shuto, S. Ueshima, L.N. Ho, H. Nishiguchi, Y. Takita, J. Ceram. Soc. Jpn. 110 (9) (2002) 801803. [13] C. Cooper, R. Burch, Water Res. 33 (18) (1999) 36893694. [14] G.J.A.A. Soler-Illia, C. Sanchez, New J. Chem. 24 (2000) 493. [15] G.J.A.A. Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem. Rev. 102 (2002) 40934138. [16] J.W. Kriesel, M.S. Sander, T.D. Tilley, Chem. Mater. 13 (2001) 3554 3563. [17] A. Bhaumik, S. Inagaki, J. Am. Chem. Soc. 123 (2001) 691696.