Abstract
Pharmaceutical contaminants such as diclofenac (DCF) cannot be removed in existing wastewater treatment facilities; therefore, studies on application of new treatment processes and improvement of efficiency are required. In this study, a modified photocatalyst doped with nitrogen and europium was prepared and the performance of DCF was evaluated. A modified photocatalyst that responds to visible light was prepared by precipitating nitrogen and europium in a TiO2 powder using a plasma-in-liquid process (PLP). The performance of the photocatalyst was evaluated by a degradation experiment of diclofenac, a pharmaceutical ingredient. The dopant tended to precipitate in proportion to the amount of precursor added, but more nitrogen precipitated than europium even when the same amount was added. Nitrogen and europium were dispersed evenly throughout the TiO2 powder, and the Ti2p peak position of the modified TiO2 photocatalyst (MTP) coincided with bare TiO2, and europium precipitated in the form of Eu2O3. The bandgap energy of the MTPs was lower than that of unmodified TiO2 photocatalyst, but the MTP with only europium precipitated was the lowest. When a blue light source in the visible region was used, DCF decomposition by MTPs was improved by about 15 to 25 times compared to bare TiO2, and europium precipitation photocatalyst had the highest DCF decomposition characteristic. In addition, MTPs showed excellent reusability properties. Four kinds of by-products were detected in the decomposition process of DCF, and three decomposition pathways by reactions such as decarboxylation, C−N cleavage and hydroxylation were considered. The final mineralization to H2O, CO2, and chlorine occurs by hydroxylation, such as by OH, on the MTP.
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References
K. A. Holloway, Expert Rev. Clin. Pharmacol., 4, 335 (2011).
J. Busfield, Soc. Sci. Med., 131, 199 (2015).
T. aus der Beek, F.-A. Weber, A. Bergmann, S. Hickmann, I. Ebert, A. Hein and A. Küster, Environ. Toxicol. Chem., 35, 823 (2016).
G. E. Swan, R. Cuthbert, M. Quevedo, R. E. Green, D. J. Pain, P. Bartels, A. A. Cunningham, N. Duncan, A. A. Meharg, J. L. Oaks, J. P. Jones, S. Shultz, M.A. Taggart, G. Verdoorn and K. Wolter, Biol. Lett., 2, 279 (2006).
R. Triebskorn, H. Casper, A. Heyd, R. Eikemper, H.-R. Köhler and J. Schwaiger, Aquat. Toxicol., 68, 151 (2004).
L. Zhang, Y. Liu and Y. Fu, RSC Adv., 10, 9907 (2020).
D. Kanakaraju, C. A. Motti, B. D. Glass and M. Oelgemoller, Environ. Chem., 11, 51 (2014).
M. Irandost, R. Akbarzadeh, M. Pirsaheb, A. Asadi, P. Mohammadi and M. Sillanpaa, J. Mol. Liq., 291, 111342 (2019).
X. Lu, Y. Shao, N. Gao, J. Chen, Y. Zhang, H. Xiang and Y. Guo, Ecotoxicol. Environ. Saf., 141, 139 (2017).
S. J. Ki, K. J. Jeon, Y. K. Park, S. Jeong, H. Lee and S. C. Jung, Catal. Today, 293, 15 (2017).
H. Lee, S. H. Park, Y. K. Park, S. J. Kim, S. G. Seo, S. J. Ki and S. C. Jung, Chem. Eng. J., 278, 259 (2015).
S. C. Jung, Water Sci. Technol., 63, 1491 (2011).
D. J. Lee, Y. K. Park, S. J. Kim, H. Lee and S. C. Jung, Korean J. Chem. Eng., 32, 1188 (2015).
Z. Hua, Z. Dai, X. Bai, Z. Ye, H. Gua and X. Huang, J. Hazard. Mater., 293, 112 (2015).
H. Lee, Y. K. Park, S. J. Kim, B. H. Kim and S. C. Jung, J. Ind. Eng. Chem., 32, 259 (2015).
Y. Zhang and Q. Li, Solid State Sci., 16, 16 (2013).
S. J. Ki, Y. K. Park, J. S. Kim, W. J. Lee, H. Lee and S. C. Jung, Chem. Eng. J., 377, 120087 (2019).
H. Lee, I. S. Park, H. J. Bang, Y. K. Park, H. Kim, H. H. Ha, B. J. Kim and S. C. Jung, Appl. Surf. Sci., 471, 893 (2019).
H. Lee, I. S. Park, H. J. Bang, Y. K. Park, E. B. Cho, B. J. Kim and S. C. Jung, Appl. Surf. Sci., 481, 625 (2019).
S. C. Kim, Y. K. Park and S. C. Jung, Korean J. Chem. Eng., 38, 885 (2021).
K. H. Chung, S. Jeong, H. Lee, S. J. Kim, K. J. Jeon, Y. K. Park and S. C. Jung, Int. J. Hydrogen Energy, 42, 24099 (2017).
H. Lee, S. H. Park, S. G. Seo, S. J. Kim, S. C. Kim, Y. K. Park and S. C. Jung, Curr. Nanosci., 10, 7 (2014).
S. C. Kim, Y. K. Park, B. H. Kim, H. Kim, W. J. Lee, H. Lee and S. C. Jung, Korean J. Chem. Eng., 35, 750 (2018).
S. Jeong, K. H. Chung, H. Lee, H. Park, K. J. Jeon, Y. K. Park and S. C. Jung, ACS Sustain. Chem. Eng., 5, 3659 (2017).
H. Lee, B. H. Kim, Y. K. Park, K. H. An, Y. J. Choi and S. C. Jung, Int. J. Hydrogen Energy, 41, 7582 (2016).
M. K. Mun, W. O. Lee, J. W. Park, D. S. Kim, G. Y. Yeom and D. W. Kim, Appl. Sci. Converg. Technol., 26, 164 (2017).
S. Pitchaimuthu, K. Honda, S. Suzuki, A. Naito, N. Suzuki, K. Katsumata, K. Nakata, N. Ishida, N. Kitamura, Y. Idemoto, T. Kondo, M. Yuasa, O. Takai, T. Ueno, N. Saito, A. Fujishima and C. Terashima, ACS Omega, 3, 898 (2018).
Y. K. Heo, M. A. Bratescu, T. Ueno and N. Saito, J. Appl. Phys., 116, 024302 (2014).
D. Ihnatiuk, C. Tossi, I. Tittonen and O. Linnik, Catalysts, 10, 1074 (2020).
S. Anwer, G. Bharath, S. Iqbal, H. Qian, T. Masood, K. Liao, W. J. Cantwell, J. Zhang and L. Zheng, Electrochim. Acta, 283, 1095 (2018).
J. Tian, H. Gao, H. Kong, P. Yang, W. Zhang and J. Chu, Nanoscale Res. Lett., 8, 533 (2013).
I. Camps, M. Borlaf, M. T. Colomer, R. Moreno, L. Duta, C. Nita, A. Perez del Pino, C. Logofatu, R. Serna and E. Gyorgy, RSC Adv., 7, 37643 (2017).
D. Chen, Z. Jiang, J. Geng, Q. Wang and D. Yang, Ind. Eng. Chem. Res., 46, 2741 (2007).
G. Yan, M. Zhang, J. Hou and J. Yang, Mater. Chem. Phys., 129, 553 (2011).
T. T. Khan, G. A. K. M. R. Bari, H. J. Kang, T. G. Lee, J. W. Park, H. J. Hwang, S. M. Hossain, J. S. Mun, N. Suzuki, A. Fujishima, J. H. Kim, H. K. Shon and Y. S. Jun, Catalysts, 11, 109 (2021).
W. Q. Liu, D. Wu, H. Chang, R. X. Duan, W. J. Wu, G. Amu, K. F. Chao, F. Q. Bao and O. Tegus, Nanomaterials, 8, 66 (2018).
C. H. Zeng, K. Zheng, K. L. Lou, X. T. Meng, Z. Q. Yan, Z. N. Ye, R. R. Su and S. Zhong, Electrochim. Acta, 165, 396 (2015).
S. A. Ansari, M. M. Khan, M. O. Ansari and M. H. Cho, New J. Chem., 40, 3000 (2016).
M. Myilsamy, M. Mahalakshmi, N. Subha, A. Rajabhuvaneswari and V. Murugesan, RSC Adv., 6, 35024 (2016).
L. Rizzo, S. Meric, D. Kassinos, M. Guida, F. Russo and V. Belgiorno, Water Res., 43, 979 (2009).
B. Di Credico, R. Bellobono, M. D’Arienzo, D. Fumagalli, M. Redaelli, R. Scotti and F. Morazzoni, Int. J. Photoenergy, 2015, 919217 (2015).
L. A. M. Lx, A. E. González S. Cipagauta-Díaz and R. Gómez, J. Chem. Technol. Biotechnol., 95, 2694 (2020).
J. Wang, D. N. Tafen, J. P. Lewis, Z. Hong, A. Manivannan, M. Zhi, M. Li and N. Wu, J. Am. Chem. Soc., 131, 12290 (2009).
D. Chen, Q. Zhu, Z. Lv, X. Deng, F. Zhou and Y. Deng, Mater. Res. Bull., 47, 3129 (2012).
S. Ramandi, M. H. Entezari and N. Ghows, Ultrason. Sonochem., 38, 234 (2017).
T. P. Nguyen, Q. B. Tran, Q. V. Ly, L. T. Hai, D. T. Le, M. B. Tran, T. T. T. Ho, X. C. Nguyen, M. Shokouhimehr, D. V. N. Vo, S. S. Lam, H. T. Do, S. Y. Kim, T. V. Tung and Q. V. Le, Arab. J. Chem., 13, 8361 (2020).
J. Xu, Y. Ao, D. Fu and C. Yuan, J. Colloid Interface Sci., 328, 447 (2008).
Z. Hu, X. Cai, Z. Wang, S. Li, Z. Wang and X. Xie, J. Hazard. Mater., 380, 120812 (2019).
H. Shi, G. Zhou, Y. Liu, Y. Fu, H. Wang and P. Wu, RSC Adv., 9, 31370 (2019).
I. Michael, A. Achilleos, D. Lambropoulou, V. Osorio Torrens, S. Pérez, M. Petrovic, D. Barceló and D. Fatta-Kassinos, Appl. Catal. B, 147, 1015 (2014).
E. Nie, M. Yang, D. Wang, X. Yang, X. Luo and Z. Zheng, Chemosphere, 113, 165 (2014).
H. Yu, E. Nie, J. Xu, S. Yan, W. J. Cooper and W. Song, Water Res., 47, 1909 (2013).
S. Salaeh, D. J. Perisic, M. Biosic, H. Kusic, S. Babic, U. L. Stangar, D. D. Dionysiou and A. L. Bozic, Chem. Eng. J., 304, 289 (2016).
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This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIT) (2021R1A2C1006315).
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Lee, H., Park, YK. & Jung, SC. Preparation of N and Eu doped TiO2 using plasma in liquid process and its photocatalytic degradation activity for diclofenac. Korean J. Chem. Eng. 39, 2080–2088 (2022). https://doi.org/10.1007/s11814-022-1093-4
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DOI: https://doi.org/10.1007/s11814-022-1093-4