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전이금속 도핑에 따른 TiO2 광촉매의 특성분석 및 광분해 효과
Effects of Transition Metal Ion Doping on the Photocatalytic Reactivity and Physical Properties of TiO2
한국가스안전공사 가스기기연구팀, 429-712 경기도 시흥시 대야동 332-1 1한국에너지기술연구원 에너지변환·저장연구센터, 305-343 대전시 유성구 장동 71-2
Gas Instrument Research Team, Korea Gas Safety Corporation, 332-1 Daeya-dong, Shihung, Gyonggi-do 429-712, Korea 1Energy Conversion and Storage Research Center, Korea Institute of Energy Research, 71-2 Jang-dong, Yusung-gu, Daejeon 305-343, Korea
parkse@kgs.or.kr
HWAHAK KONGHAK, August 2003, 41(4), 542-548(7), NONE
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Abstract
본 연구에서는 주기율표 그룹으로 나누어지는 Fe(3+), Co(2+), Ni(2+)와 Mo(5+), Nb(5+), W(6+) 각각을 TiO2에 도핑한 박막 필름의 광촉매 활성과 물성평가를 수행하여, 두 그룹간의 상관관계를 규명하고자 하였다. 제조한 시료의 광활성은 trichloroethylene(TCE)을 통하여 GC-ECD, FTIR 그리고 GC-MS를 사용하였으며, 물성측정은 XRD, SEM, UV-Vis, TG/DSC, FTIR 그리고 XPS로 수행하였다. 모든 시료는 아나타제 결정 구조로 확인되었으며, SEM 분석에 의해 약 20 nm의 두께로 코팅됨을 측정하였다. 활성비교 및 물성측정에서 두 그룹에 의한 일관된 경향이 나타났는데, Mo(5+), Nb(5+), W(6+)의 경우가 결정화도, UV 흡수율, TCE 분해율에서 Fe(3+), Co(2+), Ni(2+)의 경우보다 높게 나왔으며, 전자의 경우 XPS 분석에 의하여 다양한 산화상태가 나왔으나, 후자의 경우는 산화상태가 확인되지 않았다. 다양한 산화상태는 전자/정공 분리에 도움을 준 것으로 사료되며, 이외 모든 특성분석 값은 광화학적 활성에 도움을 주는 것으로 알려져 있는 것들이다. 전이금속 도핑의 경우 도핑 물질의 선택과 이를 통한 요구되는 물성 취득이 매우 중요한 역할 담당함을 입증하였다.
In this study, we investigate the physical properties and photocatalytic activities of TiO2 thin films doped with low valence (Fe(3+), Co(2+), and Ni(2+)) and high valence (Mo(5+), Nb(5+), and W(6+)) cations. Photocatalytic activity was measured with trichloroethylene (TCE) degradation, while films were characterized by XRD, SEM, UV-Vis, TG/DSC, FTIR, and XPS. All samples prepared were in anatase phase with 20 nm film thickness. As a result, there existed a consistency that crystallinity, UV absorption at 360 nm and TCE conversion were higher in case of high valence cations than in case of low valence cations. In addition, even though various oxidation states for Mo(5+), Nb(5+), and W(6+) were confirmed, those were not identified for Fe(3+), Co(2+), and Ni(2+) thin films. The presence of different oxidation states of dopants and a higher degree of crystallinity seems to be beneficial for retarding charge pair recombination processes in the TiO2 lattice.
Keywords
References
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Fox MA, Dulay MT, Chem. Rev., 93, 341 (1993)
Linsebigler AL, Lu GQ, Yates JT, Chem. Rev., 95(3), 735 (1995)
Bickley RI, Gonzallez-Carreno T, Palmisano L, Mater. Chem. Phys., 29, 475 (1991)
Bonamali P, Tomohiro H, Kouichi G, Gyoichi N, J. Mol. Catal. A-Chem., 169, 147 (2001)
Brinker CJ, Scherer GW, Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing, John Wiley & Sons (1990)
Pecchi G, Reyes P, Sanhueza PJ, Chemosphere, 43, 141 (2001)
Gao Y, Thin Solid Films, 346(1-2), 73 (1999)
Yu J, Zhao X, Zhao Q, Mater. Chem. Phys., 69, 25 (2001)
Xie HQ, Zhang QH, Xi TG, Wang JC, Liu Y, Thermochim. Acta, 381(1), 45 (2002)
Qin D, Chang W, Zhou J, Chen Y, Thermochim. Acta, 236, 205 (1994)
Hariaznov O, Harizanova A, Sol. Energy Mater. Sol. Cells, 63, 185 (2000)
Music S, Gotic M, Ivanda M, Povovic S, Turkocvic A, Trojko R, Sekulic A, Furic K, Mater. Sci. Eng. B, 47, 33 (1997)
Kaliwoh N, Zhang JY, Boyd IW, Surf. Coat. Technol., 125, 424 (2000)
Djaoued Y, Taj R, Bruning R, Badilescu S, Ashrit PV, Bader G, Vo-Van T, J. Non-Cryst. Solids, 297, 55 (2002)
Socrates G, Infrared Characteristics Group Frequencies, John Wiley & Sons, New York (1980)
Pal B, Sharon M, Nogami G, Mater. Chem. Phys., 59, 254 (1999)
Ivanova T, Harizanova A, Solid State Ion., 138(3-4), 227 (2001)
Palmisano L, Augugliaro V, Sclafani A, Schiavello M, J. Phys. Chem., 92, 6710 (1988)
Wagner CD, Riggs WM, Davis LE, Moulders JF, Mullenberg GE, Handbook of X-ray Photoelectron Spectroscopy, edited by Mullenberg, G.E., Perkin-Elmer Corporation, Eden Prairie, MN (1979)
Spevack PA, McIntyre NS, J. Phys. Chem., 97, 11020 (1993)
Galtayries A, Wisniewski S, Grimblot J, J. Electron Spectroscopy Related Phenomena, 87, 31 (1997)
Jong AM, Borg HJ, IJzendoorn LJ, Soudant VGFM, Beer VHJ, Veen JAR, Niemantsverdriet JW, J. Phys. Chem., 97, 6477 (1993)
Murata Y, Fukuta S, Ishikawa S, Yokoyama S, Sol. Energy Mater. Sol. Cells, 62, 157 (2000)
Gao Y, Thevuthasan S, McCready DE, Engelhard M, J. Cryst. Growth, 212, 178 (2000)
Atashbar MZ, Sun HT, Gong B, Wlodarski W, Lamb R, Thin Solid Films, 326(1-2), 238 (1998)
Colton RI, Rabalais JW, Inorg. Chem., 15, 236 (1976)
Su L, Dai Q, Lu Z, Spectrochim. Acta : A, 55, 2179 (1999)
Siokou A, Leftheriotis G, Papaefthimiou S, Yianoulis P, Surf. Sci., 482-485, 294 (2001)
Colton J, Wayne J, Inorg. Chem., 15, 236 (1976)
Choi WY, Termin A, Hoffmann MR, J. Phys. Chem., 98(51), 13669 (1994)
Gratzel M, Howe RF, J. Phys. Chem., 94, 2566 (1990)
Serpone N, Lawless D, Disdier J, Herrmann JM, Langmuir, 10(3), 643 (1994)
Karakitsou KE, Verykios XE, J. Phys. Chem., 97, 1184 (1993)
