Ecology and Resilient Infrastructure

응용생태공학회 (Korean Society of Ecology and Infrastructure Engineering)
권호 표지
DOI QR코드

DOI QR Code

TiO2 나노입자 광촉매 반응에 의한 비스페놀 A의 분해 제거 및 독성 저감

Photocatalytic Degradation and Detoxification of Bisphenol A Using TiO2 Nanoparticles

  • 조아영 (고려대학교 환경생태공학부) ;
  • 정진호 (고려대학교 환경생태공학부)
  • Jo, A-Yeong (Division of Environmental Science and Ecological Engineering, Korea University) ;
  • Jung, Jinho (Division of Environmental Science and Ecological Engineering, Korea University)
  • 투고 : 2015.12.05
  • 심사 : 2015.12.20
  • 발행 : 2015.12.30
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

본 논문은 수용액에서 $TiO_2$ 나노입자 (Degussa P25) 광촉매 반응에 의한 비스페놀 A (BPA)의 분해 제거를 연구하였다. 3시간의 광촉매 반응 (자외선 파장 = 365 nm, 자외선 강도 = $3mW\;cm^{-2}$, $TiO_2$ 농도 = $2.0g\;L^{-1}$)에 의하여 98%의 BPA ($1.0{\times}10^{-5}M$)와 89%의 총유기탄소가 제거되었다. 그리고 광분해, 가수분해와 흡착반응에 의한 BPA의 분해 제거는 각각 2%, 5%와 13%로 나타났다. 광촉매 반응에 의한 BPA의 분해 제거는 수산화 라디칼의 소광제인 메탄올의 농도가 증가 할수록 감소하였다. 이것은 BPA와 수산화 라디칼의 반응이 BPA 분해 제거의 주요한 기작이라는 것을 나타낸다. 이 반응의 초기 유사 1차 속도 상수는 $7.94{\times}10^{-4}min^{-1}$로 계산되었으며, BPA 90%를 분해 제거하는 시간은 25분으로 나타났다. 그리고 광촉매 반응에 의한 BPA의 독성 저감을 평가하기 위하여 물벼룩 (Daphnia magna, 생후 24시간 미만)을 이용한 급성독성 시험을 실시하였다. 물벼룩에 대한 BPA의 급성독성 (48시간)은 초기 2.93 TU (독성 단위)였으며, 3시간의 광촉매 반응 후에는 무독성으로 나타났다. 이것은 BPA의 광촉매 반응에서 독성 분해산물이 생성되지 않는 다는 것을 제시한다.

Photocatalytic degradation of bisphenol A (BPA) in aqueous solution was investigated using $TiO_2$ nanoparticles (Degussa P25) in this study. After a 3 hr photocatalytic reaction (${\lambda}=365nm$ and $I=3mW\;cm^{-2}$, $[TiO_2]=2.0g\;L^{-1}$), 98% of BPA ($1.0{\times}10^{-5}M$) was degraded and 89% of the total organic carbon was removed. In addition, BPA degradation by photolytic, hydrolytic and adsorption reactions was found to be 2%, 5% and 13%, respectively. The reaction rate of BPA degradation by photocatalysis decreased with increasing concentration of methanol that is used as a hydroxyl radical scavenger. This indicates that the reaction between BPA and hydroxyl radical was the key mechanism of BPA degradation. The pseudo-first-order reaction rate constant for this reaction was determined to be $7.94{\times}10^{-4}min^{-1}$, and the time for 90% BPA removal was found to be 25 min. In addition, acute toxicity testing using Daphnia magna neonates (< 24 h old) was carried out to evaluate the reduction of BPA toxicity. Acute toxicity (48 hr) to D. magna was decreased from 2.93 TU (toxic unit) to non-toxic after photocatalytic degradation of BPA for 3 hr. This suggests that there was no formation of toxic degradation products from BPA photocatalysis.

키워드

참고문헌

  1. Bistan, M., Tisler, T. and Pintar, A. 2012. Catalytic and photocatalytic oxidation of aqueous bisphenol A solutions: removal, toxicity and estrogenicity. Industrial & Engineering Chemistry Research 51: 8826-8834 https://doi.org/10.1021/ie201957z
  2. Brennan, S.J., Brougham, C.A., Roche, J.J. and Fogarty, A.M. 2006. Multi-generational effects of four selected environmental oestrogens on Daphnia magna. Chemosphere 64: 49-55. https://doi.org/10.1016/j.chemosphere.2005.11.046
  3. Caspers, N. 1998. No estrogenic effects of bisphenol A in Daphnia magna Straus. Bulletin of Environmental Contamination and Toxicology 61: 143-148. https://doi.org/10.1007/s001289900741
  4. Chen, Y., Yang, S., Wang, K. and Lou, L. 2005. Role of primary active species and $TiO_2$ surface characteristic in UV-illuminated photodegradation of acid orange 7. Journal of Photochemistry and Photobiology A: Chemistry 172: 47-54. https://doi.org/10.1016/j.jphotochem.2004.11.006
  5. Cheng, S., Tsai, S.-J and Lee, Y.-F. 1995. Photocatalytic decomposition of phenol over titanium oxide of various structures. Catalysis Today 26: 87-96. https://doi.org/10.1016/0920-5861(95)00071-M
  6. Chiang, K., Lim, T.M., Tsen, L. and Lee, C.C. 2004. Photocatalytic degradation and mineralization of bisphenol A by $TiO_2$ and platinized $TiO_2$. Applied Catalysis A: General 261: 225-237. https://doi.org/10.1016/j.apcata.2003.11.004
  7. Daskalaki, V.M., Frontistis, Z., Mantzavinos, D. and Katsaounis, A. 2011. Solar light-induced degradation of bisphenol A with $TiO_2$ immobilized on Ti. Catalysis Today 161: 110-114. https://doi.org/10.1016/j.cattod.2010.09.018
  8. D'Oliveira, J.C., Al-Sayyed, G. and Pichat, P. 1990. Photodegradation of 2- and 3-chlorophenol in titanium dioxide aqueous suspensions. Environmental Science & Technology 24: 990-996. https://doi.org/10.1021/es00077a007
  9. Fujishima, A., Rao, T.N. and Tryk, D.A. 2000. Titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 1: 1-21. https://doi.org/10.1016/S1389-5567(00)00002-2
  10. Ishibashi, K., Fujishima, A., Watanabe, T. and Hashimoto, K. 2000. Quantum yields of active oxidative species formed on $TiO_2$ photocatalyst. Journal of Photochemistry and Photobiology A: Chemistry 134: 139-142. https://doi.org/10.1016/S1010-6030(00)00264-1
  11. ISO. 2012. Water Quality - Determination of the Inhibition of the Mobility of Daphnia magna Straus (Cladocera, Crustacea) - Acute Toxicity Test. ISO 6341:2012, International Organization for Standardization, Geneva, Switzerland.
  12. Ji, Y., Zhou, L., Ferronato, C., Yang, X., Salvador, A., Zeng, C. and Chovelon, J.M. 2013. Photocatalytic degradation of atenolol in aqueous titanium dioxide suspensions: kinetics, intermediates and degradation pathways. Journal of Photochemistry and Photobiology A: Chemistry 254: 35-44. https://doi.org/10.1016/j.jphotochem.2013.01.003
  13. Jia, C., Wang, Y., Zhang, C., Qin, Q., Kong, S. and Yao, S.K. 2012. Photocatalytic degradation of bisphenol A in aqueous suspensions of titanium dioxide. Environmental Engineering Science 29: 630-637. https://doi.org/10.1089/ees.2011.0132
  14. Jo, J.E. 2004. Photocatalytic-photooxidation of Aquatic Bisphenol A Solution using $TiO_2$ Film Coated on Loess Ball. M.Sc. Thesis, Chosun University, Gwangju, Korea. (in Korean)
  15. Linsebigler, A.L., Lu, G. and Yates Jr., J.T. 1995. Photocatalysis on $TiO_2$ surfaces: principles, mechanisms, and selected results. Chemical Reviews 95: 735-758. https://doi.org/10.1021/cr00035a013
  16. Matthews, R.W. 1986. Photo-oxidation of organic material in aqueous suspensions of titanium dioxide. Water Research 20: 569-578. https://doi.org/10.1016/0043-1354(86)90020-5
  17. OECD. 2004. Daphnia sp. Acute Immobilisation Test. Guideline for Testing of Chemicals No. 202. Paris, France.
  18. Tao, H., Hao, S., Chang, F., Wang, L., Zhang, Y. and Cai, X. 2011. Photodegradation of bisphenol A by titana nanoparticles in mesoporous MCM-41. Water, Air, & Soil Pollution 214: 491-498. https://doi.org/10.1007/s11270-010-0440-y
  19. Thomas, J. 1965. Rates of reaction of the hydroxyl radical. Transactions of the Faraday Society 61: 702-707. https://doi.org/10.1039/tf9656100702
  20. Wang, R., Ren, D., Xia, S., Zhang, Y. and Zhao, J. 2009. Photocatalytic degradation of bisphenol A (BPA) using immobilized $TiO_2$ and UV illumination in a horizontal circulating bed photocatalytic reactor (HCBPR). Journal of Hazardous Materials 169: 926-932. https://doi.org/10.1016/j.jhazmat.2009.04.036
  21. Weber, C.I. 1991. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. Environmental Monitoring Systems Laboratory, Office of Research and Development, US Environmental Protection Agency, EPA/821/R-02/012, Washington DC, USA
  22. Yeo, M.K. and Kang, M. 2006. Photodecomposition of bisphenol A on nanometer-sized $TiO_2$ thin film and the associated biological toxicity to zebrafish (Danio rerio) during and after photocatalysis. Water Research 40: 1906-1914. https://doi.org/10.1016/j.watres.2005.12.034