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Enhanced photocatalytic activity of TiO2@mercapto-functionalized silica toward colored organic dyes

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Abstract

Core–shell-type TiO2@mercaptopropyl-functionalized silica (MPS) particles were prepared for enhanced photocatalytic performance of TiO2. The MPS particles were adopted in the composite-type photocatalyst design so as to enhance the photo-catalytic activity through the chemical interaction between chemically modified substrate particles and organic dye molecules, although they do not have photocatalytic activity. Three organic dyes, rhodamine B, rhodamine 6G, and methyl orange, were selected for testing dye adsorption characteristics and photocatalytic activities of the TiO2@MPS particles, commercial P25, and unsupported TiO2 nanosols. Rhodamine B and rhodamine 6G dyes were adsorbed much more on the TiO2@MPS particles than P25, by factors of 6 and 43, respectively, while methyl orange molecules were adsorbed more readily on P25. Such difference in the dye adsorption characteristics of the two photocatalysts may be related with available functional groups and the dyes. This would lead to enhanced photocatalytic degradation of the dyes because of combined chemical and physical adsorption mechanisms. Toward the two rhodamine dyes, the TiO2@MPS particles show significantly enhanced photocatalytic activity per TiO2 than P25 under both UV and visible light irradiation. Especially under visible irradiation, the degradation rate constants of rhodamine B and rhodamine 6G molecules per TiO2 were higher, 18 and 45 times, respectively, for the TiO2@MPS particles than for P25. Toward methyl orange dye, the degradation rate constant per TiO2 was lower for the TiO2@MPS particles than for P25 under UV irradiation but it was eight times higher under visible irradiation. The TiO2@MPS particles were recyclable and their photocatalytic activity did not change at all at least for three repeated photo-degradation tests.

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References

  1. Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238:37–38

    Article  Google Scholar 

  2. Kabra K, Chaudhary R, Sawhney RL (2004) Treatment of hazardous organic and inorganic compounds through aqueous-phase photocatalysis: a review. Ind Eng Chem Res 43:7683–7696

    Article  Google Scholar 

  3. Malato S, Fernández-Ibáñez P, Maldonado MI, Blanco J, Gernjak W (2009) Decontamination and disinfection of water by solar photocatalysis: recent overview and trends. Catal Today 147:1–59

    Article  Google Scholar 

  4. Gaya UI, Abdullah AH (2008) Heterogeneous photocatalytic degradation of organic contaminants over titanium dioxide: a review of fundamentals, progress and problems. J Photochem Photobiol C 9:1–12

    Article  Google Scholar 

  5. Linsebigler AL, Lu G, Yates JT (1995) Photocatalysis on TiO2 surfaces: principes, mechanisms, and selected results. Chem Rev 95:735–758

    Article  Google Scholar 

  6. Nakata K, Fujishima A (2012) TiO2 photocatalysis: design and applications. J Photochem Photobiol C 13:169–189

    Article  Google Scholar 

  7. Pelaez M, Nolan NT, Pillai SC et al (2012) A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl Catal B 125:331–349

    Article  Google Scholar 

  8. Konstantinou IK, Albanis TA (2004) TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations a review. Appl Catal B 49:1–14

    Article  Google Scholar 

  9. Turchi CS, Ollis DF (1990) Photocatalytic degradation of organic water contaminants: mechanisms involving hydroxyl radical attack. J Catal 122:178–192

    Article  Google Scholar 

  10. Chen LH, Li XY, Deng Z et al (2013) Hydrothermal and surfactant treatment to enhance the photocatalytic activity of hierarchically meso-macroporous titanias. Catal Today 212:89–97

    Article  Google Scholar 

  11. Kao LH, Hsu TC, Lu HY (2007) Sol–gel synthesis and morphological control of nanocrystalline TiO2 via urea treatment. J Colloid Interface Sci 316:160–167

    Article  Google Scholar 

  12. Ong WJ, Tan LL, Chai SP, Yong ST, Mohamed AR (2014) Facet-dependent photocatalytic properties of TiO2-based composites for energy conversion and environmental remediation. ChemSusChem 7:690–719

    Article  Google Scholar 

  13. Han X, Kuang Q, Jun M, Xie Z, Zheng L (2009) Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties. J Am Chem Soc 131:3152–3153

    Article  Google Scholar 

  14. Pang YL, Abdullah AZ (2013) Effect of carbon and nitrogen co-doping on characteristics and sonocatalytic activity of TiO2 nanotues catalyst for degradation of rhodamine B in water. Chem Eng J 214:129–138

    Article  Google Scholar 

  15. Ohno T, Akiyoshi M, Umebayashi T, Asai K, Mitsui T, Matsumura M (2004) Preparation of S-doped TiO2 photocatalysts and their photocatalytic activites under visible light. Appl Catal A 265:115–121

    Article  Google Scholar 

  16. Umebayashi T, Yamaki T, Tanaka S, Asai K (2003) Visible light-induced degradation of methylene blue on S-doped TiO2. Chem Lett 32:330–331

    Article  Google Scholar 

  17. RA, Morikawa T, Ohwaki T, Aoki K, Taga Y (2001) Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293:269–271

    Article  Google Scholar 

  18. Cong Y, Zhang K, Chen F, Anpo M (2007) Synthesis and characterization of nitrogen-doped TiO2 nanophotocatalyst with high visible light activity. J Phys Chem C 111:6976–6982

    Article  Google Scholar 

  19. Mahlambi MM, Mishra AK, Mishra SB, Krause RW, Mamba BB, Raichur AM (2013) Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light. J Nanosci Nanotechnol 13:4934–4942

    Article  Google Scholar 

  20. Fukugaichi S, Henmi T, Matsue N (2013) Facile synthesis of TiO2-zeolite composite and its enhanced photocatalytic activity. Catal Lett 143:1255–1259

    Article  Google Scholar 

  21. Liu H, Dong X, Wang X, Sun C, Li J, Zhu Z (2013) A green and direct synthesis of graphene oxide encapsulated TiO2 core/shell structures with enhanced photoactivity. Chem Eng J 230:279–285

    Article  Google Scholar 

  22. Zhang H, Lv X, Li Y, Wang Y, Li J (2010) P25-graphene composite as a high performance photocatalyst. ACS Nano 4:380–386

    Article  Google Scholar 

  23. Muthirulan P, Devi CN, Sundaram MM (2014) TiO2 wrapped graphene as a high performance photocatalyst for acid orange 7 dye degradation uner solar/UV light irradiations. Ceram Int 40:5945–5957

    Article  Google Scholar 

  24. Meng H, Hou W, Xu X, Xu J, Zhang X (2014) TiO2-loaded activated carbon fiber: hydrothermal snythesis, adsorption properties and photocatalytic activity under visible light irradation. Particuology 14:38–43

    Article  Google Scholar 

  25. Zhou W, Pan K, Qu Y et al (2010) Photodegradation of organic contamination in wastewaters by bonding TiO2/single-walled carbon nanotube composites with enhanced photocatalytic activity. Chemosphere 81:555–561

    Article  Google Scholar 

  26. Lim SH, Phonthammachai N, White SSPTJ (2008) Simple route to monodispersed silica–titania core–shell photocatalysts. Langmuir 24:6226–6231

    Article  Google Scholar 

  27. Hu JL, Qian HS, Li JJ, Hu Y, Li ZQ, Yu SH (2013) Synthesis of mesoporous SiO2@TiO2 core–shell nanospheres with enhanced photocatalytic properties. Part Part Syst Charact 30:306–310

    Article  Google Scholar 

  28. Kim SK, Chang H, Cho K et al (2011) Enhanced photocatalytic property of nanoporous TiO2/SiO2 microparticles prepared by aerosol assisted co-assembly of nanoparticles. Mater Lett 65:3330–3332

    Article  Google Scholar 

  29. Anderson C, Bard AJ (1995) An improved photocatalyst of TiO2/SiO2 prepared by a sol–gel synthesis. J Phys Chem 99:9882–9885

    Article  Google Scholar 

  30. Lee JW, Othman MR, Eom Y, Lee TG, Kim WS, Kim J (2008) The effects of sonification and TiO2 deposition on the micro-characteristrics of the thermally treated SiO2/TiO2 spherical core-shell particles for photo-catalysis of methyl orange. Microporous Mesoporous Mater 116:561–568

    Article  Google Scholar 

  31. Xu J, Xiao X, Stepanov AL et al (2013) Efficiency enhancements in Ag nanoparticles-SiO2-TiO2 sandwiched structure via plasmonic effect-enhanced light capturing. Nanoscale Res Lett 8:73

    Article  Google Scholar 

  32. Zhang X, Zhu Y, Yang X et al (2013) Enhanced visible light photocatalytic activity of interlayer-isolatedd triplex Ag@SiO2@TiO2 core–shell nanoparticles. Nanoscale 5:3359–3366

    Article  Google Scholar 

  33. Chen F, Zhao J, Hidaka H (2003) Highly selective deethylation of rhodamine B: adsorption and photooxidation pathways of the dye on the TiO2/SiO2 composite photocatalyst. Int J Photoenergy 5:209–217

    Article  Google Scholar 

  34. Kim JS, Kim SJ, Jung EG, Yun HH, Koo SM (2013) The preparation of titania nano crystals and silica–titania core–shell particles through peptization process. J Ceram Process Res 14:327–331

    Google Scholar 

  35. Wu T, Liu G, Zhao J, Hidaka H, Serpone N (1998) Photoassisted degradation of dye pollutants. V. Self-photosensitized oxidative transformation of rhodamine B under visible light irradiation in aqueous TiO2 dispersions. J Phys Chem B 102:5848–5851

    Google Scholar 

  36. Yu K, Yang S, He H, Sun C, Gu C, Ju Y (2009) Visible light-driven photocatalytic degradation of rhodamine B over NaBiO3: pathways and mechanism. J Phys Chem A 113:10024–10032

    Article  Google Scholar 

  37. Wang Q, Chen C, Zhao D, Ma W, Zhao J (2008) Change of adsorption modes of dyes on fluorinated TIO2 and its effect on photocatalytic degradation of dyes under visible irradiation. Langmuir 24:7338–7345

    Article  Google Scholar 

  38. Sung-Suh HM, Choi JR, Hah HJ, Koo SM, Bae YC (2004) Comparison of Ag deposition effects on the photocatalytic activity of nanoparticulate TiO2 under visible and UV light irradiation. J Photochem Photobiol A 163:37–44

    Article  Google Scholar 

  39. Lubec G (1996) The hydroxyl radical: from chemistry to human disease. J Investig Med 44:324–346

    Google Scholar 

  40. Khodja AA, Sehili T, Pilichowski J-F, Boule P (2001) Photocatalytic degradation of 2-phenylphenol on TiO2 and ZnO in aqueous suspensions. J Photochem Photobiol A 141:231–239

    Article  Google Scholar 

  41. Daneshvar N, Salari D, Khataee AR (2003) Photocatalytic degradation of azo dye acid red 14 in water: investigation of the effect of operational parameters. J Photochem Photobiol, A 157:111–116

    Article  Google Scholar 

  42. Battino R, Rettich TR, Tominaga T (1983) The solubility of oxygen and ozone in liquids. J Phys Chem Ref Data 12:163–178

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Human Resources Development Program (NO. 20094020200010) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Trade, Industry and Energy and also supported by Nano-Convergence Foundation (www.nanotech2020.org) funded by the Ministry of Science, ICT and Future Planning (MSIP, Korea) & the Ministry of Trade, Industry and Energy(MOTIE, Korea) (Project Name: 1415131476) and Hanyang Science and Technology Scholarship Program.

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Authors and Affiliations

  1. Department of Chemical Engineering, Hanyang University, Seoul, 133-791, Korea

    Hwan Hui Yun, Jung Soo Kim, Euk Hyun Kim, Hyung Jun Lim & Sang Man Koo

  2. Department of Fuel Cells and Hydrogen Technology, Hanyang University, Seoul, 133-791, Korea

    Sang Kyoung Lee, Jin Woo Kim & Sang Man Koo

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  1. Hwan Hui Yun
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Correspondence to Sang Man Koo.

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Yun, H.H., Kim, J.S., Kim, E.H. et al. Enhanced photocatalytic activity of TiO2@mercapto-functionalized silica toward colored organic dyes. J Mater Sci 50, 2577–2586 (2015). https://doi.org/10.1007/s10853-015-8823-5

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