화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.22, No.4, 445-456, April, 2014
DOI10.1007/s13233-014-2062-5  Export Citation
Simple Synthesis of Water-Dispersible and Photoactive Titanium Dioxide Nanoparticles Using Functionalized Poly(ethylene oxide)s
Seung-Hoon Bahng, Nan Hyun Kwon, Hyung Cheol Kim, Abu Bakkar Siddique, Ho-Jung Kang, Jae Yeol Lee, Joohoon Kim, Sehoon Kim1, and Jungahn Kim†
  • Department of Chemistry, Kyung Hee University, Seoul, 130-701, Korea
  • 1Theragnostic Center, KIST, Seoul, 136-791, Korea
E-mail:
Versatile and direct synthesis of water-dispersible titanium dioxide (TiO2) nanoparticles in the presence of functionalized poly(ethylene oxide)s (PEO) having carboxylic acid groups is presented. The functionalized PEOs, such as PEO-folate conjugate and PEO-b-poly(maleic acid) (PEO-b-PMAc) as polymeric surfactants, were employed for in situ synthesis of TiO2 nanoparticles through hydrolytic sol-gel process of titanium tetrachloride as a precursor in eco-friendly alcoholic media at a relatively low temperature. Both of the two polymers were found to be very effective for stabilizing TiO2 nanocrystals, exhibiting not only fairly good photocatalytic activities but also water-dispersible property. The core TiO2 crystallites in the size range of 8~11 nm could be readily controlled in ethanol at a relatively low reaction temperature (70℃), irrespective of the incipient reaction condition, which showed mixed polymorphs. The TiO2 nanoparticles consist of a few percentages (<10%) of brookite and mostly anatase phases. This process provides a simple and useful in situ preparative route to obtain water-dispersible TiO2 nanoparticles.
Keywords:simple synthesis;titanium dioxide nanoparticles;photocatalytic activity;functionalized poly(ethylene oxide)s.
  1. Nel A, Xia T, Madler L, Li N, Science, 311, 622 (2006)
  2. Talapin DV, Lee JS, Kovalenko MV, Shevchenko EV, Chem. Rev., 110(1), 389 (2010)
  3. Raveendran P, Fu J, Wallen SL, J. Am. Chem. Soc., 125(46), 13940 (2003)
  4. Panacek A, Kvitek L, Prucek R, Kolar M, Vecerova R, Pizurova N, Sharma VK, Nevecna T, Zboril R, J. Phys. Chem. B, 110(33), 16248 (2006)
  5. Sun RWY, Chen R, Chung NPY, Ho CM, Lin CLS, Che CM, Chem. Commun., 5059 (2005)
  6. Xiong HM, Xu Y, Ren OG, Xia YY, J. Am. Chem. Soc., 130(24), 7522 (2008)
  7. Yang PD, Zhao DY, Margolese DI, Chmelka BF, Stucky GD, Nature, 396(6707), 152 (1998)
  8. Cho WS, Kang BC, Lee JK, Jeong J, Che JH, Seok SH, Part. Fibre Toxicol., 10, 9 (2013)
  9. Yao J, Wang C, Int. J. Photoenergy, 643182 (2010)
  10. Shi H, Magaye R, Castranova V, Zhao J, Part. Fibre Toxicol., 10, 15 (2013)
  11. Weir A, Westerhoff P, Fabricius L, Hristovski K, von Goetz N, Environ. Sci. Technol., 46, 2242 (2012)
  12. Wang J, Zhou G, Chen C, Yu H, Wang T, Ma Y, Jia G, Gao Y, Li B, Sun J, Li Y, Jiao F, Zhao Y, Chai Z, Toxicol. Lett., 168, 176 (2007)
  13. Teow Y, Asharani PV, Hande MP, Valiyaveettil S, Chem. Commun., 47, 7025 (2011)
  14. Kang TS, Smith AP, Taylor BE, Durstock MF, Nano Lett., 9, 601 (2009)
  15. Karthikeyan CS, Wietasch H, Thelakkat M, Adv. Mater., 19(8), 1091 (2007)
  16. Werts MPL, Badila M, Brochon C, Hebraud A, Hadziioannou G, Chem. Mater., 20, 1292 (2008)
  17. Seo J, Chung H, Kim M, Lee J, Choi I, Cheon J, Small, 3, 850 (2007)
  18. Thevenot P, Cho J, Wavhal D, Timmons RB, Tang L, Nanomedicine, 4, 226 (2008)
  19. Blake DM, Maness PC, Huang Z, Wolfrum EJ, Huang J, Jacoby WA, Sep. Purif. Methods, 28(1), 1 (1999)
  20. Tedja R, Lim M, Amal R, Marquis C, ACS nano, 6, 4083 (2013)
  21. Reyes-Coronado D, Rodriguez-Gattorno G, Espinosa-Pesqueira ME, Cab C, de Coss R, Oskam G, Nanotechnology, 19, 145605 (2008)
  22. Li JG, Ishigaki T, Sun X, J. Phys. Chem. C, 111, 4969 (2007)
  23. Dinh CT, Ngugyen TD, Kleitz F, Do TO, ACS nano, 3, 3737 (2009)
  24. Tokuhisa H, Hammond PT, Adv. Funct. Mater., 13(11), 831 (2003)
  25. Guerrero G, Mutin PH, Vioux A, Chem. Mater., 13, 4367 (2001)
  26. Sugimoto T, Zhou XP, Muramatsu A, J. Colloid Interface Sci., 259(1), 43 (2003)
  27. Liufu S, Xiao H, Li Y, J. Colloid Interface Sci., 281, 55 (2005)
  28. Gui S, Sang X, Zheng L, Ze Y, Zhao X, Sheng L, Sun Q, Cheng Z, Cheng J, Hu R, Wang L, Hong F, Tang M, Part. Fibre Toxicol., 10, 4 (2013)
  29. Niederberger M, Garnweitner G, Krumeich F, Nesper R, Colfen H, Antoniett M, Chem. Mater., 16, 1202 (2004)
  30. Kotsokechagia T, Cellesi F, Thomas A, Niederberger M, Tirelli N, Langmuir, 24(13), 6988 (2008)
  31. Edler KJ, Hawley AM, O’Driscoll BMD, Schweins R, Chem. Mater., 22, 4579 (2010)
  32. Gnauck M, Jaehne E, Blaettler T, Tosatti S, Textor M, Adler HJP, Langmuir, 23(2), 377 (2007)
  33. Yamaguchi S, Kobayashi H, Narita T, Kanehira K, Sonezaki S, Kudo N, Kubota Y, Terasaka S, Houkin K, Ultrason. Sonochem., 18, 1197 (2011)
  34. Yamaguchi S, Kobayashi H, Narita T, Kanehira K, Sonezaki S, Kubota Y, Terasaka S, Iwasaki Y, Photochem. Photobiol., 86, 964 (2010)
  35. Kim TH, Kim K, Park GH, Choi JH, Lee S, Kang HJ, Lee JY, Kim J, Macromol. Res., 17(10), 770 (2009)
  36. Maeng JH, Lee DH, Jung KH, Bae YH, Park IS, Jeong S, Jeon YS, Shim CK, Kim W, Kim J, Lee J, Lee YM, Kim JH, Kim WH, Hong SS, Biomaterials, 31, 4995 (2010)
  37. Kwark YJ, Kim J, Novak BM, Macromol. Res., 15(1), 31 (2007)
  38. Gilman H, Cartledge FK, J. Organomet. Chem., 2, 447 (1964)
  39. Kim J, Lee S, Nam JH, Cho YJ, Kim J, Lee JY, Kang HJ, Kim S, Kim HT, Park HM, Kim J, Macromol. Res., 19(7), 716 (2011)
  40. Jun YW, Casula MF, Sim JH, Kim SY, Cheon J, Alivisatos AP, J. Am. Chem. Soc., 125(51), 15981 (2003)
  41. Pan J, Liu G, Lu GQ, Cheng HM, Angew. Chem.-Int. Edit., 50, 2133 (2011)
  42. Yang HG, Sun CH, Qiao SZ, Zou J, Liu G, Smith SC, Cheng HM, Lu GQ, Nature, 453, 638 (2008)
  43. Selloni A, Nat. Mater., 7(8), 613 (2008)
  44. Maliakal A, Katz H, Cotts PM, Subramoney S, Mirau P, J. Am. Chem. Soc., 127(42), 14655 (2005)
  45. Beek WJE, Janssen RAJ, Adv. Funct. Mater., 12(8), 519 (2002)
  46. Othman SH, Rashid SA, Ghazi TIM, Abdullah N, J. Nanomater., 718214 (2012)
  47. Yu JG, Su YR, Cheng B, Zhou MH, J. Mol. Catal. A-Chem., 258(1-2), 104 (2006)
  48. Chens H, Ma J, Hao Z, Qi L, Chem. Mater., 7, 663 (1995)
  49. Han Y, Kim HS, Kim H, J. Nanomater., 427453 (2012)
  50. Cozzoli PD, Komowski A, Weller H, J. Am. Chem. Soc., 126, 14539 (2003)
  51. Wu X, Wang D, Yang S, J. Colloid Interface Sci., 222, 37 (2007)
  52. Pettibone JM, Cwiertny DM, Scherer M, Grassian VH, Langmuir, 24(13), 6659 (2008)
  53. Andronic L, Perniu D, Duta A, J. Sol-Gel Sci. Technol., 66, 472 (2013)
  54. Wisniewska M, Chibowski S, Urban T, React. Funct. Polym., 72(11), 791 (2012)
  55. Jokerst JV, Lobovkina T, Zare RN, Gambhir SS, Nanomedicine, 6, 715 (2011)
  56. Lorente C, Thomas AH, Acc. Chem. Res., 39, 395 (2006)
  57. Rajh T, Chen LX, Lukas K, Liu T, Thurnauer MC, Tiede DM, J. Phys. Chem. B, 106(41), 10543 (2002)
  58. Ohno Y, Tomita K, Komatsubara Y, Taniguchi T, Katsumata K, Matsushita N, Kogure T, Okada K, Cryst. Growth Des., 11, 4831 (2011)
  59. Pottier A, Cassaignon S, Chaneac C, Villain F, Tronc E, Jolivet JP, J. Mater. Chem., 13, 877 (2003)
  60. Tomitta K, Petrykin V, Kobayashi M, Shiro M, Yoshimura M, Kakihana M, Angew. Chem.-Int. Edit., 45, 2378 (2006)
  61. Mattsson A, Osterlund L, J. Phys. Chem. C, 114, 14121 (2010)
  62. Chen HH, Nanayakkara CE, Grassian VH, Chem. Rev., 112(11), 5919 (2012)
  63. Mehrvar M, Anderson WA, Moo-Young M, Int. J. Photoenergy, 4, 141 (2002)
  64. Velegraki T, Poulios I, Charalabaki M, Kalogerakis N, Samaras P, Mantzavinos D, Appl. Catal. B: Environ., 62(1-2), 159 (2006)
  65. Jiang J, Oberdorster G, Biswas P, J. Nanopart. Res., 11, 77 (2009)
  66. Xiao J, Chen WQ, Wang FYK, Du JZ, Macromolecules, 46(2), 375 (2013)
  67. Lee WA, Pernodet N, Li B, Lin CH, Hatchwell E, Rafailovich MH, Chem. Commun., 4815 (2007)
  68. Hall SR, Swinerd VM, Newby FN, Collins AM, Mann S, Chem. Mater., 18, 598 (2006)
  69. Singh S, Mahalingam H, Singh PK, Appl. Catal. A: Gen., 462-463, 178 (2013)
  70. Sokmen M, Tatlidil I, Breen C, Clegg F, Buruk CK, Sivlim T, Akkan S, J. Hazard. Mater., 187(1-3), 199 (2011)
  71. Tanaka K, Capule MFV, Hisanaga T, Chem. Phys. Lett., 187, 73 (1991)
  72. Zhang QL, Du LC, Weng YX, Wang L, Chen HY, Li JQ, J. Phys. Chem. B, 108(39), 15077 (2004)
  73. Park H, Park Y, Kim W, Choi W, J. Photochem. Photobiol. C-Photochem. Rev., 15, 1 (2013)
  74. Hoffmann MR, Martin ST, Choi WY, Bahnemann DW, Chem. Rev., 95(1), 69 (1995) 
  75. Guillard C, Lachheb H, Houas A, Ksibi M, Elaloui E, Herrmann JM, J. Photochem. Photobiol. A-Chem., 158, 27 (2003)
  76. Madhu GM, Raj MALA, Pai KVK, J. Environ. Biol., 30, 259 (2009)
  77. Zhang AP, Sun YP, World J. Gastroentrol., 10, 3191 (2004)
  78. Mano SS, Kanehira K, Sonezaki S, Taniguchi A, Int. J. Mol. Sci., 13(3), 3703 (2012)
  79. Zhang Y, Wu L, Zeng Q, Zhi J, J. Phys. Chem. C, 112, 16457 (2008)
  80. Li YZ, Lee NH, Hwang DS, Song JS, Lee EG, Kim SJ, Langmuir, 20(25), 10838 (2004)
  81. Kwark YJ, Kim J, Novak BM, Macromol. Res., 15(1), 31 (2007)
  82. Maeng JH, Lee DH, Jung KH, Bae YH, Park IS, Jeong S, Jeon YS, Shim CK, Kim W, Kim J, Lee J, Lee YM, Kim JH, Kim WH, Hong SS, Biomaterials, 31, 4995 (2010)
  83. Kim J, Lee S, Nam JH, Cho YJ, Kim J, Lee JY, Kang HJ, Kim S, Kim HT, Park HM, Kim J, Macromol. Res., 19(7), 716 (2011)
  84. Nakayama N, Hayashi T, Colloids Surf. A: Physicochem. Eng. Asp., 317, 543 (2008)