Synthesis of TiO2 from Beach Sand Ilmenite and Its Photocatalytic Activity

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2010 Vol.47, Issue 3 Preview Page Next Page

Synthesis of TiO₂ from Beach Sand Ilmenite and Its Photocatalytic Activity 해사 티탄철광으로부터 TiO₂ 합성 및 광촉매 활성: 김진수, 한요셉, 박재구, 신희영, 문지웅
Jinsoo Kim, Yosep Han, Jaikoo Park, Heeyoung Shin and Jiwoong Moon

30 June 2010. pp. 359-368

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Abstract

Rutile TiO2 was synthesized by using beach sand ilmenite. Synthesis of TiO2 was accomplished via mechano-chemical treatment of ilmenite and subsquent simultaneous leaching and hydrolysis in dilute solutions of hydrochloric acid. The microstructure of synthetic product was investigated by SEM, TEM and physicochemical characteristics of synthetic products for different heat treatment temperature were analyzed by XRD, BET, EDS, TGA, FT-IR. And the photocatalytic activity of synthetic product and commercial TiO2 was evaluated by methylene blue decomposition according to the irradiation time under UV-A light source. As a result, the optimum heat treatment temperature of synthetic product was 700℃.

Keywords

Beach sand

Ilmenite

TiO2

Photocatalytic catalyst

해사 티탄철광을 이용하여 rutile상의 TiO2를 합성하였다. TiO2의 합성은 티탄철광의 메카노케미컬 처리와 HCl 용액 상에서의 추출 및 가수분해 반응으로 이루어졌다. 합성물의 미세구조는 SEM과 TEM을 통해 관찰하였고, 합성물의 다양한 열처리 온도에 따른 물리･화학적 특성을 XRD, BET, EDS, TGA, FT-IR로 분석 하였다. 또한 합성물과 상용 TiO2의 광촉매 활성을 UV-A 광원 하에서 시간에 따른 메틸렌블루 분해능을 통해 평가하였다. 이러한 결과로부터 합성물의 최적 열처리 온도는 700℃로 판단되었다.

키워드

해사

티탄철광

TiO2

광촉매

References

Amer, A.M., 2002, “Alkaline pressure leaching of mechanically activated Rosetta ilmenite concentrate,” Hydrometallurgy, Vol. 67, No. 1-3, pp. 125-133.
Barrett, E.P., Joyner, L.G. and Halenda, P.P., 1951, “The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms,” J. Am. Chem. Soc., Vol. 73, No. 1, pp. 373-380.
Bentrup, U., Brückner, A., Fait, M., Kubias, B. and Stelzer, J.B., 2006, “Structure-reactivity relationships in VOx/TiO2 catalysts for the oxyhydrative scission of 1-butene and n-butane to acetic acid as examined by in situ-spectroscopic methods and catalytic tests,” Catal. Today., Vol. 112, No. 1-4, pp. 78-81.
Bokhimi, X., Morales, A., Aguilar, M., Toledo-Antonio, J.A. and Pedraza, F., 2001, “Local order in titania polymorphs,” Int. J. Hydrogen. Ene., Vol. 26, No. 12, pp. 1279-1287.
Brunnauer, S., Emmett, P.H. and Teller, E., 1938, “Adsorption of Gases in Multimolecular Layers,” J. Am. Chem. Soc., Vol. 60, pp. 309-319.
Cheng, H., Ma, J., Zhao, Z. and Qi, L., 1995, “Hydrothermal Preparation of Uniform Nanosize Rutile and Anatase Particles,” Chem. Mater., Vol. 7, No. 4, pp. 663-671.
Chuan, X.Y., Hirano, M. and Inagaki, M., 2004, “Preparation and photocatalytic performance of anatase-mounted natural porous silica, pumice, by hydrolysis under hydrothermal conditions,” Appl. Catal. B-Environ., Vol. 51, No. 4, pp. 255-260.
Cullity, B.D. and Stock, S.R., 2001, Elements of X-Ray Diffraction, 3rd Ed., Prentice-Hall, Massachusetts, USA.
El-Khaliny, N.M., 1967, Preparation of titanium dioxide from the Egyptian ilmenite ore, MS thesis, Faculty of Science, Ain Shams University, Cairo, Egypt.
Fujishima, A., Rao, T.N. and Tryk, D.A., 2000, “Titanium dioxide photocatalysis,” J. Photoch. Photobio. B., Vol. 1, No. 1, pp. 1-21.
Hanada, N., Ichikawa, T., Orimo, S.I. and Fujii, H., 2004, “Correlation between hydrogen storage properties and structural characteristics in mechanically milled magnesium hydride MgH2,” J. Alloy. Compd., Vol. 366, No. 1-2, pp. 269-273.
Herrmann, J.M. and Guillard, C., 2000, “Photocatalytic degradation of pesticides in agricultural used waters,” C. R. Acad. Sci. Paris., Vol. 3, No. 6, pp. 417-422.
Juhasz, A.Z. and Opoczky, L., 1990, Mechanical activation of minerals by grinding pulverizing and morphology of particles, Halsted Press, New York, United States.
Kim, D.S. and Kwak, S.Y., 2007, “The hydrothermal synthesis of mesoporous TiO2 with high crystallinity, thermal stability, large surface area, and enhanced photocatalytic activity,” Appl. Catal. A-Gen., Vol. 323, pp. 110-118.
Kim, D.S., Han, S.J. and Kwak, S.Y., 2007, “Synthesis and photocatalytic activity of mesoporous TiO2 with the surface area, crystallite size, and pore size,” J. Colloid. Interf. Sci., Vol. 316, No. 1, pp. 85-91.
Kolen’ko, Y.V., Churaqulov, B.R., Kunst, M., Mazerolles, L. and Colbeau-Justin, C., 2004, “Photocatalytic properties of titania powders prepared by hydrothermal method,” Appl. Catal. B-Environ., Vol. 54, No. 1, pp. 51-58.
Larbot, A., Alary, J.A., Fabre, J.P., Guizard, C. and Cot, L., 1986, “Microporous layers from sol-gel techniques,” Mater. Res. Soc. Symp. Proc., Vol. 73, pp. 659-664.
Lasheen, T.A.I., 2005, “Chemical benefication of Rosetta ilmenite by direct reduction leaching,” Hydrometallurgy., Vol. 76, No. 1-2, pp. 123-129.
Li, X.Z. and Zhao, Y.G., 1999, “Advanced treatment of dyeing wastewater for reuse,” Water. Sci. Technol., Vol. 39, No. 10, pp. 249-255.
Liu, J., Huang, X., Duan, J., Ai, H. and Tu, P., 2005, “A low-temperature synthesis of multiwhisker-based zinc oxide micron crystals,” Mater. Lett., Vol. 59, No. 28, pp. 3710-3714.
Lu, Z.Y. and Muir, D.M., 1988, “Dissolution of metal ferrites and iron oxides by HCl under oxidizing and reducing conditions,” Hydrometallurgy., Vol. 21, No. 1, pp. 9-21.
Mccormick, P.G., 1995, “Application of mechnical alloying to chemical refining,” Mater. Trans. Jim., Vol. 36, No. 2, pp. 161-169.
Ng, Y.H., Ikeda, S., Harada, T., Higashida, S., Sakata, T., Mori, H. and Matsumura, M., 2007, “Fabrication of Hollow Carbon Nanospheres Encapsulating Platinum Nanoparticles Using a Photocatalytic Reaction,” Adv. Mater., Vol. 19, No. 4, pp. 597-601.
Ovenstone, J. and Yanagisawa, K., 1999, “Effect of Hydrothermal Treatment of Amorphous Titania on the Phase Change from Anatase to Rutile during Calcination,” Chem. Mater., Vol. 11, No. 10, pp. 2770-2774.
Peiro, A.M., Doyle, G., Mills, A. and Durrant, J.R., 2005, “Freestanding Polymer-Metal Oxide Nanocomposite Films for Light-Driven Oxygen Scavenging,” Adv. Mater., Vol. 17, No. 19, pp. 2365-2368.
Peng, T., Zhao, D., Dai, K., Shi, W. and Hirao, K., 2005, “Synthesis of Titanium Dioxide Nanoparticles with Mesoporous Anatase Wall and High Photocatalytic Activity,” J. Phys. Chem. A., Vol. 109, No. 11, pp. 4947-4952.
Porter, J.F., Li, Y.G. and Chan, C.K., 1999, “The effect of calcination on the microstructural characteristics and photoreactivity of Degussa P-25 TiO2,” J. Mater. Sci., Vol. 34, No. 7, pp. 1523-1531.
Puddu, V., Choi, H., Dionysiou, D.D. and Puma, G.L., 2009, “TiO2 photocatalyst for indoor air remediation: Influence of crystallinity, crystal phase, and UV radiation intensity on trichloroethylene degradation,” Appl. Catal. B-Environ., http://www.elsevier.com/locate/apcatb.
Sclafani, A., Palmisano, L. and Schiavello, M., 1990, “Influence of the Preparation Methods of titanium dioxide on the Photocatalytic Degradation of Phenol on Aqueous Dispersion,” J. Phys. Chem., Vol. 94, No. 2, pp. 829-835.
Shin, H.Y., 2009, “Research Report: The Development of Technology for Recovering of the Valuable Minerals from Beach Sand.” Tan, R., He, Y., Zhu, Y., Xu, B. and Cao, L., 2003, “Hydrothermal preparation of mesoporous TiO2 powder from Ti(SO4)2 with poly (ethylene glycol) as template,” J. Mater. Sci., Vol. 38, No. 19, pp. 3973-3978.
Tian, G., Fu, H., Jing, L. and Tian, C., 2009, “Synthesis and photocatalytic activity of stable nanocrystalline TiO2 with high crystallinity and large surface area,” J. Hazard. Mater., Vol. 161, No. 2-3, pp. 1122-1130.
Tkacova, K. and Balaz, P., 1996, “Reactivity of mechanically activated chalcopyrite,” Int. J. Miner. Process., Vol. 44-45, pp. 197-208.
Van Dyk, J.P., Vegter, N.M. and Pistorius, P.C., 2002, “Kinetics of ilmenite dissolution in hydrochloric acid,” Hydrometallurgy., Vol. 65, No. 1, pp. 31-36.
Wang, J.J., Zhang, M., Wang, K., Zhang, J.W., Wu, Z.S. and Jin, Z.S., 2008, “Reasons for the deactivation of Pt0/TiO2 photocatalyst treated by inert gas N2,” Appl. Surf. Sci., Vol. 254, No. 17, pp. 5375-5379.
Welham, N.J. and Llewellyn, D.J., 1998, “Mechanical Enhancement of the Dissolution of Iimenite,” Miner. Eng., Vol. 11, No. 9, pp. 827-841.
Wu, M., Lin, G., Chen, D., Wang, G., He, D., Feng, S. and Xu, R., 2002, “Sol-Hydrothermal Synthesis and Hydrothermally Structural Evolution of Nanocrystal Titanium Dioxide,” Chem. Mater., Vol. 14, No. 5, pp. 1974-1980.
Yan, X.L., Ohno, T., Nishijima, K., Abe, R. and Ohtani, B., 2006, “Is methylene blue an appropriate substrate for a photocatalytic activity test? A study with visible-light responsive titania,” Chem. Phys. Lett., Vol. 429, No. 4-6, pp. 606-610.
Yang, J., Chen, C.C., Ji, H.W., Ma, W.H. and Zhao, J.C., 2005, “Mechanism of TiO2-Assisted Photocatalytic Degradation of Dyes under Visible Irradiation: Photoelectrocatalytic Study by TiO2-Film Electrodes,” J. Phys. Chem. B., Vol. 109, No. 46, pp. 21900-21907.
Yamazaki, S., Yoshida, A. and Abe, H., 2005, “Photocatalytic degradation of chloroform in the gas phase on the porous TiO2 pellets: effect of Cl accumulated on the catalyst surface,” J. Photochem. Photobiol. A., Vol. 169, No. 2, pp. 191-196.
Zhu, J., Zheng, W., He, B., Zhang, J. and Anpo, M., 2004, “Characterization of Fe-TiO2 photocatalysts synthesized by hydrothermal method and their photocatalytic reactivity for photodegradation of XRG dye diluted in water,” J. Mol. Catal. A-Chem., Vol. 216, No. 1, pp. 35-43.

Information

Publisher :The Korean Society of Mineral and Energy Resources Engineers
Publisher(Ko) :한국자원공학회
Journal Title :Journal of the Korean Society for Geosystem Engineering
Journal Title(Ko) :한국지구시스템공학회지
Volume : 47
No :3
Pages :359-368

[1] Amer, A.M., 2002, “Alkaline pressure leaching of mechanically activated Rosetta ilmenite concentrate,” Hydrometallurgy, Vol. 67, No. 1-3, pp. 125-133.

[2] Barrett, E.P., Joyner, L.G. and Halenda, P.P., 1951, “The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms,” J. Am. Chem. Soc., Vol. 73, No. 1, pp. 373-380.

[3] Bentrup, U., Brückner, A., Fait, M., Kubias, B. and Stelzer, J.B., 2006, “Structure-reactivity relationships in VOx/TiO2 catalysts for the oxyhydrative scission of 1-butene and n-butane to acetic acid as examined by in situ-spectroscopic methods and catalytic tests,” Catal. Today., Vol. 112, No. 1-4, pp. 78-81.

[4] Bokhimi, X., Morales, A., Aguilar, M., Toledo-Antonio, J.A. and Pedraza, F., 2001, “Local order in titania polymorphs,” Int. J. Hydrogen. Ene., Vol. 26, No. 12, pp. 1279-1287.

[5] Brunnauer, S., Emmett, P.H. and Teller, E., 1938, “Adsorption of Gases in Multimolecular Layers,” J. Am. Chem. Soc., Vol. 60, pp. 309-319.

[6] Cheng, H., Ma, J., Zhao, Z. and Qi, L., 1995, “Hydrothermal Preparation of Uniform Nanosize Rutile and Anatase Particles,” Chem. Mater., Vol. 7, No. 4, pp. 663-671.

[7] Chuan, X.Y., Hirano, M. and Inagaki, M., 2004, “Preparation and photocatalytic performance of anatase-mounted natural porous silica, pumice, by hydrolysis under hydrothermal conditions,” Appl. Catal. B-Environ., Vol. 51, No. 4, pp. 255-260.

[8] Cullity, B.D. and Stock, S.R., 2001, Elements of X-Ray Diffraction, 3rd Ed., Prentice-Hall, Massachusetts, USA.

[9] El-Khaliny, N.M., 1967, Preparation of titanium dioxide from the Egyptian ilmenite ore, MS thesis, Faculty of Science, Ain Shams University, Cairo, Egypt.

[10] Fujishima, A., Rao, T.N. and Tryk, D.A., 2000, “Titanium dioxide photocatalysis,” J. Photoch. Photobio. B., Vol. 1, No. 1, pp. 1-21.

[11] Hanada, N., Ichikawa, T., Orimo, S.I. and Fujii, H., 2004, “Correlation between hydrogen storage properties and structural characteristics in mechanically milled magnesium hydride MgH2,” J. Alloy. Compd., Vol. 366, No. 1-2, pp. 269-273.

[12] Herrmann, J.M. and Guillard, C., 2000, “Photocatalytic degradation of pesticides in agricultural used waters,” C. R. Acad. Sci. Paris., Vol. 3, No. 6, pp. 417-422.

[13] Juhasz, A.Z. and Opoczky, L., 1990, Mechanical activation of minerals by grinding pulverizing and morphology of particles, Halsted Press, New York, United States.

[14] Kim, D.S. and Kwak, S.Y., 2007, “The hydrothermal synthesis of mesoporous TiO2 with high crystallinity, thermal stability, large surface area, and enhanced photocatalytic activity,” Appl. Catal. A-Gen., Vol. 323, pp. 110-118.

[15] Kim, D.S., Han, S.J. and Kwak, S.Y., 2007, “Synthesis and photocatalytic activity of mesoporous TiO2 with the surface area, crystallite size, and pore size,” J. Colloid. Interf. Sci., Vol. 316, No. 1, pp. 85-91.

[16] Kolen’ko, Y.V., Churaqulov, B.R., Kunst, M., Mazerolles, L. and Colbeau-Justin, C., 2004, “Photocatalytic properties of titania powders prepared by hydrothermal method,” Appl. Catal. B-Environ., Vol. 54, No. 1, pp. 51-58.

[17] Larbot, A., Alary, J.A., Fabre, J.P., Guizard, C. and Cot, L., 1986, “Microporous layers from sol-gel techniques,” Mater. Res. Soc. Symp. Proc., Vol. 73, pp. 659-664.

[18] Lasheen, T.A.I., 2005, “Chemical benefication of Rosetta ilmenite by direct reduction leaching,” Hydrometallurgy., Vol. 76, No. 1-2, pp. 123-129.

[19] Li, X.Z. and Zhao, Y.G., 1999, “Advanced treatment of dyeing wastewater for reuse,” Water. Sci. Technol., Vol. 39, No. 10, pp. 249-255.

[20] Liu, J., Huang, X., Duan, J., Ai, H. and Tu, P., 2005, “A low-temperature synthesis of multiwhisker-based zinc oxide micron crystals,” Mater. Lett., Vol. 59, No. 28, pp. 3710-3714.

[21] Lu, Z.Y. and Muir, D.M., 1988, “Dissolution of metal ferrites and iron oxides by HCl under oxidizing and reducing conditions,” Hydrometallurgy., Vol. 21, No. 1, pp. 9-21.

[22] Mccormick, P.G., 1995, “Application of mechnical alloying to chemical refining,” Mater. Trans. Jim., Vol. 36, No. 2, pp. 161-169.

[23] Ng, Y.H., Ikeda, S., Harada, T., Higashida, S., Sakata, T., Mori, H. and Matsumura, M., 2007, “Fabrication of Hollow Carbon Nanospheres Encapsulating Platinum Nanoparticles Using a Photocatalytic Reaction,” Adv. Mater., Vol. 19, No. 4, pp. 597-601.

[24] Ovenstone, J. and Yanagisawa, K., 1999, “Effect of Hydrothermal Treatment of Amorphous Titania on the Phase Change from Anatase to Rutile during Calcination,” Chem. Mater., Vol. 11, No. 10, pp. 2770-2774.

[25] Peiro, A.M., Doyle, G., Mills, A. and Durrant, J.R., 2005, “Freestanding Polymer-Metal Oxide Nanocomposite Films for Light-Driven Oxygen Scavenging,” Adv. Mater., Vol. 17, No. 19, pp. 2365-2368.

[26] Peng, T., Zhao, D., Dai, K., Shi, W. and Hirao, K., 2005, “Synthesis of Titanium Dioxide Nanoparticles with Mesoporous Anatase Wall and High Photocatalytic Activity,” J. Phys. Chem. A., Vol. 109, No. 11, pp. 4947-4952.

[27] Porter, J.F., Li, Y.G. and Chan, C.K., 1999, “The effect of calcination on the microstructural characteristics and photoreactivity of Degussa P-25 TiO2,” J. Mater. Sci., Vol. 34, No. 7, pp. 1523-1531.

[28] Puddu, V., Choi, H., Dionysiou, D.D. and Puma, G.L., 2009, “TiO2 photocatalyst for indoor air remediation: Influence of crystallinity, crystal phase, and UV radiation intensity on trichloroethylene degradation,” Appl. Catal. B-Environ., http://www.elsevier.com/locate/apcatb.

[29] Sclafani, A., Palmisano, L. and Schiavello, M., 1990, “Influence of the Preparation Methods of titanium dioxide on the Photocatalytic Degradation of Phenol on Aqueous Dispersion,” J. Phys. Chem., Vol. 94, No. 2, pp. 829-835.

[30] Shin, H.Y., 2009, “Research Report: The Development of Technology for Recovering of the Valuable Minerals from Beach Sand.” Tan, R., He, Y., Zhu, Y., Xu, B. and Cao, L., 2003, “Hydrothermal preparation of mesoporous TiO2 powder from Ti(SO4)2 with poly (ethylene glycol) as template,” J. Mater. Sci., Vol. 38, No. 19, pp. 3973-3978.

[31] Tian, G., Fu, H., Jing, L. and Tian, C., 2009, “Synthesis and photocatalytic activity of stable nanocrystalline TiO2 with high crystallinity and large surface area,” J. Hazard. Mater., Vol. 161, No. 2-3, pp. 1122-1130.

[32] Tkacova, K. and Balaz, P., 1996, “Reactivity of mechanically activated chalcopyrite,” Int. J. Miner. Process., Vol. 44-45, pp. 197-208.

[33] Van Dyk, J.P., Vegter, N.M. and Pistorius, P.C., 2002, “Kinetics of ilmenite dissolution in hydrochloric acid,” Hydrometallurgy., Vol. 65, No. 1, pp. 31-36.

[34] Wang, J.J., Zhang, M., Wang, K., Zhang, J.W., Wu, Z.S. and Jin, Z.S., 2008, “Reasons for the deactivation of Pt0/TiO2 photocatalyst treated by inert gas N2,” Appl. Surf. Sci., Vol. 254, No. 17, pp. 5375-5379.

[35] Welham, N.J. and Llewellyn, D.J., 1998, “Mechanical Enhancement of the Dissolution of Iimenite,” Miner. Eng., Vol. 11, No. 9, pp. 827-841.

[36] Wu, M., Lin, G., Chen, D., Wang, G., He, D., Feng, S. and Xu, R., 2002, “Sol-Hydrothermal Synthesis and Hydrothermally Structural Evolution of Nanocrystal Titanium Dioxide,” Chem. Mater., Vol. 14, No. 5, pp. 1974-1980.

[37] Yan, X.L., Ohno, T., Nishijima, K., Abe, R. and Ohtani, B., 2006, “Is methylene blue an appropriate substrate for a photocatalytic activity test? A study with visible-light responsive titania,” Chem. Phys. Lett., Vol. 429, No. 4-6, pp. 606-610.

[38] Yang, J., Chen, C.C., Ji, H.W., Ma, W.H. and Zhao, J.C., 2005, “Mechanism of TiO2-Assisted Photocatalytic Degradation of Dyes under Visible Irradiation: Photoelectrocatalytic Study by TiO2-Film Electrodes,” J. Phys. Chem. B., Vol. 109, No. 46, pp. 21900-21907.

[39] Yamazaki, S., Yoshida, A. and Abe, H., 2005, “Photocatalytic degradation of chloroform in the gas phase on the porous TiO2 pellets: effect of Cl accumulated on the catalyst surface,” J. Photochem. Photobiol. A., Vol. 169, No. 2, pp. 191-196.

[40] Zhu, J., Zheng, W., He, B., Zhang, J. and Anpo, M., 2004, “Characterization of Fe-TiO2 photocatalysts synthesized by hydrothermal method and their photocatalytic reactivity for photodegradation of XRG dye diluted in water,” J. Mol. Catal. A-Chem., Vol. 216, No. 1, pp. 35-43.

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