Environmental Science and Pollution Research

, Volume 25, Issue 10, pp 10090–10101 | Cite as

Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine

  • Zhiyong Bai
  • Jianlong Wang
  • Qi Yang
Research Article


Sulfonamide antibiotics are ubiquitous pollutants in aquatic environments due to their large production and extensive application. In this paper, the iron doped fibrous-structured silica (KCC-1) nanospheres (Fe-KCC-1) was prepared, characterized, and applied as a catalyst for catalytic ozonation of sulfamethazine (SMT). The effects of ozone dosage, catalyst dosage, and initial concentration of SMT were examined. The experimental results showed that Fe-KCC-1 had large surface area (464.56 m2 g−1) and iron particles were well dispersed on the catalyst. The catalyst had high catalytic performance especially for the mineralization of SMT, with mineralization ratio of about 40% in a wide pH range. With addition of Fe-KCC-1, the ozone utilization increased nearly two times than single ozonation. The enhancement of SMT degradation was mainly due to the surface reaction, and the increased mineralization of SMT was due to radical mechanism. Fe-KCC-1 was an efficient catalyst for SMT degradation in catalytic ozonation system.


Catalytic ozonation Sulfamethazine PPCPs Catalyst AOPs 


Funding information

The research was supported by the National Natural Science Foundation of China (51338005) and the Program for Changjiang Scholars and Innovative Research Team in University (IRT-13026).


  1. Afzal S, Quan X, Chen S, Wang J, Muhammad D (2016) Synthesis of manganese incorporated hierarchical mesoporous silica nanosphere with fibrous morphology by facile one-pot approach for efficient catalytic ozonation. J Hazard Mater 318:308–318. CrossRefGoogle Scholar
  2. Babić S, Zrnčić M, Ljubas D, Ćurković L, Škorić I (2015) Photolytic and thin TiO2 film assisted photocatalytic degradation of sulfamethazine in aqueous solution. Environ Sci Pollut R 22(15):11372–11386. CrossRefGoogle Scholar
  3. Bai ZY, Yang Q, Wang JL (2016a) Catalytic ozonation of sulfamethazine using Ce0.1Fe0.9OOH as catalyst: mineralization and catalytic mechanisms. Chem Eng J 300:169–176. CrossRefGoogle Scholar
  4. Bai ZY, Yang Q, Wang JL (2016b) Fe3O4/multi-walled carbon nanotubes as an efficient catalyst for catalytic ozonation of p-hydroxybenzoic acid. Int J Environ Sci Technol 13(2):483–492. CrossRefGoogle Scholar
  5. Bai ZY, Yang Q, Wang JL (2016c) Catalytic ozonation of sulfamethazine antibiotics using Ce0.1Fe0.9OOH: catalyst preparation and performance. Chemosphere 161:174–180. CrossRefGoogle Scholar
  6. Bertoluzza A, Fagnano C, Morelli MA, Gottardi V, Guglielmi M, (1982) Raman and infraredspectra on silica-gel evolving toward glass. J Non-Cryst Solids 48:117–128.CrossRefGoogle Scholar
  7. Bing J, Hu C, Nie Y, Yang M, Qu J (2015) Mechanism of catalytic ozonation in Fe2O3/Al2O3@SBA-15 aqueous suspension for destruction of ibuprofen. Environ Sci Technol 49(3):1690–1697. CrossRefGoogle Scholar
  8. Chen CM, Chen HS, Guo X, Guo SH, Yan GX (2014a) Advanced ozone treatment of heavy oil refining wastewater by activated carbon supported iron oxide. J Ind Eng Chem 20(5):2782–2791. CrossRefGoogle Scholar
  9. Chen J, Wen W, Kong L, Tian S, Ding F, Xiong Y (2014b) Magnetically separable and durable MnFe2O4 for efficient catalytic ozonation of organic pollutants. Ind Eng Chem Res 53(15):6297–6306. CrossRefGoogle Scholar
  10. Chen CM, Yoza BA, Wang YD, Wang P, Li QX, Guo SH (2015) Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O3 catalyst. Environ Sci Pollut Res 22(7):5552–5562. CrossRefGoogle Scholar
  11. Dai QZ, Wang J, Yu J, Chen J, Chen J (2014) Catalytic ozonation for the degradation of acetylsalicylic acid in aqueous solution by magnetic CeO2 nanometer catalyst particles. Appl. Catal. B: Environ 144:686–693CrossRefGoogle Scholar
  12. Davis ME, Lobo RF (1992) Zeolite and molecular sieve synthesis. Chem Mater 4(4):756–768. CrossRefGoogle Scholar
  13. Davis PJ, Jeffrey Brinker C, Smith DM, Assink RA (1992) Pore structure evolution in silica gel during aging/drying II. Effect of pore fluids. J Non-Cryst Solids 142:197–207. CrossRefGoogle Scholar
  14. Díaz-Cruz MS, García-Galán MJ, Barceló D (2008) Highly sensitive simultaneous determination of sulfonamide antibiotics and one metabolite in environmental waters by liquid chromatography–quadrupole linear ion trap–mass spectrometry. J Chromatogr A 1193(1-2):50–59. CrossRefGoogle Scholar
  15. Dong ZP, Le X, Li X, Zhang W, Dong C, Ma J (2014) Silver nanoparticles immobilized on fibrous nano-silica as highly efficient and recyclable heterogeneous catalyst for reduction of 4-nitrophenol and 2-nitroaniline. Appl Catal B Environ 159:129–135CrossRefGoogle Scholar
  16. Fan X, Restivo J, Órfão JJM, Pereira MFR, Lapkin AA (2014) The role of multiwalled carbon nanotubes (MWCNTs) in the catalytic ozonation of atrazine. Chem Eng J 241:66–76. CrossRefGoogle Scholar
  17. Fan Y, Ji Y, Kong D, Lu J, Zhou Q (2015) Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process. J Hazard Mater 300:39–47. CrossRefGoogle Scholar
  18. Faria PCC, Órfão JJM, Pereira MFR (2008) Activated carbon catalytic ozonation of oxamic and oxalic acids. Appl Catal B Environ 79(3):237–243. CrossRefGoogle Scholar
  19. Feng Y, Liu J, Wu D, Zhou Z, Deng Y, Zhang T, Shih K (2015) Efficient degradation of sulfamethazine with CuCo2O4 spinel nanocatalysts for peroxymonosulfate activation. Chem Eng J 280:514–524. CrossRefGoogle Scholar
  20. Fihri A, Cha D, Bouhrara M, Almana N, Polshettiwar V (2012) Fibrous nano-silica (KCC-1)-supported palladium catalyst: suzuki coupling reactions under sustainable conditions. Chem Sus Chem 5(1):85–89. CrossRefGoogle Scholar
  21. Gao J, Pedersen JA (2005) Adsorption of sulfonamide antimicrobial agents to clay minerals. Environ Sci Technol 39(24):9509–9516. CrossRefGoogle Scholar
  22. Gary L, Schmitt DJP (1985) Liquid chromatographic separation of inorganic anions on an alumina column. Anal Chem (12):2247–2253Google Scholar
  23. Giri RR, Ozaki H, Ota S, Takanami R, Taniguchi S (2010) Degradation of common pharmaceuticals and personal care products in mixed solutions by advanced oxidation techniques. Int J Environ Sci Technol 7(2):251–260. CrossRefGoogle Scholar
  24. Gupta VK, Agarwal S, Saleh TA (2011) Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes. Water Res 45(6):2207–2212. CrossRefGoogle Scholar
  25. Halling-Sorensen B, Nielsen SN, Lanzky PF, Ingerslev F, Liitzhof HCH, Jorgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment—a review. Chemosphere 36(2):357–393. CrossRefGoogle Scholar
  26. Huang RH, Yan H, Li L, Deng D, Shu Y, Zhang Q (2011) Catalytic activity of Fe/SBA-15 for ozonation of dimethyl phthalate in aqueous solution. Appl Catal B Environ 106:264–271Google Scholar
  27. Huang YX, Cui CC, Zhang DF, Li L, Pan D (2015) Heterogeneous catalytic ozonation of dibutyl phthalate in aqueous solution in the presence of iron-loaded activated carbon. Chemosphere 119:295–301. CrossRefGoogle Scholar
  28. Ikhlaq A, Brown DR, Kasprzyk-Hordern B (2012) Mechanisms of catalytic ozonation on alumina and zeolites in water: formation of hydroxyl radicals. Appl Catal B Environ 123-124:94–106. CrossRefGoogle Scholar
  29. Kasprzyk-Hordern B, Ziółek M, Nawrocki J (2003) Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. Appl Catal B Environ 46(4):639–669. CrossRefGoogle Scholar
  30. Legube B, Vel K (1999) Catalytic ozonation: a promising advanced oxidation technology for water treatment. Catal Today 53(1):61–72. CrossRefGoogle Scholar
  31. Liu YK, Wang JL, (2014) Radiation-induced removal of sulphadiazine antibiotics from wastewater. Environ Technol 35: 2028–2034.CrossRefGoogle Scholar
  32. Liu YK, Wang JL (2013) Degradation of sulfamethazine by gamma irradiation in the presence of hydrogen peroxide. J Hazard Mater 250-251:99–105. CrossRefGoogle Scholar
  33. Liu YK, Hu J, Wang JL (2014) Fe2+ enhancing sulfamethazine degradation in aqueous solution by gamma irradiation. Radiat Phys Chem 96:81–87. CrossRefGoogle Scholar
  34. Lv A, Hu C, Nie Y, Qu J (2012) Catalytic ozonation of toxic pollutants over magnetic cobalt-doped Fe3O4 suspensions. Appl Catal B: Environ 118:246–252CrossRefGoogle Scholar
  35. Ma ZC, Zhu L, Lu XY, Xing ST, Wu YS, Gao YZ (2014) Catalytic ozonation of p-nitrophenol over mesoporous Mn–Co–Fe oxide. Sep Purif Technol 133:357–364. CrossRefGoogle Scholar
  36. Nawrocki J, Kasprzyk-Hordern B (2010) The efficiency and mechanisms of catalytic ozonation. Appl Catal B Environ 99(1-2):27–42. CrossRefGoogle Scholar
  37. Park B, Guo W, Cui X, Park J, Ha C (2003) Preparation and characterization of organo-modified SBA-15 by using polypropylene glycol as a swelling agent. Micropor Mesopor Mater 66(2-3):229–238. CrossRefGoogle Scholar
  38. Park J, Choi H, Cho J (2004a) Kinetic decomposition of ozone and para-chlorobenzoic acid (pCBA) during catalytic ozonation. Water Res 38(9):2285–2292. CrossRefGoogle Scholar
  39. Park JS, Choi HJ, Ahn KH, Kang JW (2004b) Removal mechanism of natural organic matter and organic acid by ozone in the presence of goethite. Ozone Sci Eng 26(2):141–151. CrossRefGoogle Scholar
  40. Pérez-Moya M, Graells M, Castells G, Amigó J, Ortega E, Buhigas G, Pérez LM, Mansilla HD (2010) Characterization of the degradation performance of the sulfamethazine antibiotic by photo-Fenton process. Water Res 44(8):2533–2540. CrossRefGoogle Scholar
  41. Polshettiwar V, Cha D, Zhang X, Basset JM (2010) High-surface-area silica nanospheres (KCC-1) with a fibrous morphology. Angew Chem Inte Ed 49(50):9652–9656. CrossRefGoogle Scholar
  42. Qu RJ, Xu BZ, Meng LJ, Wang LS, Wang ZY (2015) Ozonation of indigo enhanced by carboxylated carbon nanotubes: performance optimization, degradation products, reaction mechanism and toxicity evaluation. Water Res 68:316–327. CrossRefGoogle Scholar
  43. Raman NK, Anderson MT, Brinker CJ (1996) Template-based approaches to the preparation of amorphous, nanoporous silicas. Chem Mater 8:1682–1701CrossRefGoogle Scholar
  44. Ren YM, Dong Q, Feng J, Ma J, Wen Q, Zhang ML (2012) Magnetic porous ferrospinel NiFe2O4: a novel ozonation catalyst with strong catalytic property for degradation of di-n-butyl phthalate and convenient separation from water. J Colloid Interf Sci 382(1):90–96. CrossRefGoogle Scholar
  45. Rosal R, Rodríguez A, Gonzalo MS, García-Calvo E (2008) Catalytic ozonation of naproxen and carbamazepine on titanium dioxide. Appl Catal B Environ 84(1-2):48–57. CrossRefGoogle Scholar
  46. Sable SS, Ghute PP, Álvarez P, Beltrán FJ, Medina F, Contreras S (2015) FeOOH and derived phases: efficient heterogeneous catalysts for clofibric acid degradation by advanced oxidation processes (AOPs). Catal Today 240:46–54. CrossRefGoogle Scholar
  47. Somiya S, Roy R (2000) Hydrothermal synthesis of fine oxide powders. B Mater Sci 23(6):453–460. CrossRefGoogle Scholar
  48. Sreethawong T, Chavadej S (2008) Color removal of distillery wastewater by ozonation in the absence and presence of immobilized iron oxide catalyst. J Hazard Mater 155(3):486–493. CrossRefGoogle Scholar
  49. Sui MH, Sheng L, Lu KX, Tian F (2010) FeOOH catalytic ozonation of oxalic acid and the effect of phosphate binding on its catalytic activity. Appl Catal B Environ 96(1-2):94–100. CrossRefGoogle Scholar
  50. Wan Z, Wang JL (2016) Ce-Fe-reduced graphene oxide nanocomposite as an efficient catalyst for sulfamethazine degradation in aqueous solution. Environ Sci Pollut Res 23(18):18542–18551. CrossRefGoogle Scholar
  51. Wan Z, Wang JL (2017) Degradation of sulfamethazine using Fe3O4-Mn3O4/reduced graphene oxide hybrid as Fenton-like catalyst. J Hazard Mater 324(Pt B):653–664. CrossRefGoogle Scholar
  52. Wang JL, Bai ZY (2017) Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater. Chem Eng J 312:79–98. CrossRefGoogle Scholar
  53. Wang JL, Chu LB (2016) Irradiation treatment of pharmaceutical and personal care products (PPCPs) in water and wastewater: an overview. Radiat Phys Chem 125:56–64CrossRefGoogle Scholar
  54. Wang JL, Wang SZ (2016) Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review. J Environ Manag 182:620–640. CrossRefGoogle Scholar
  55. Wang JL, Wang SZ (2018) Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chem Eng J 334:1502–1517. CrossRefGoogle Scholar
  56. Wang JL, Xu LJ (2012) Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application. Crit Rev Environ Sci Technol 42(3):251–325. CrossRefGoogle Scholar
  57. Xiong Z, Lai B, Yuan Y, Cao J, Yang P, Zhou Y (2016) Degradation of p-nitrophenol (PNP) in aqueous solution by a micro-size Fe0/O3 process (mFe0/O3): optimization, kinetic, performance and mechanism. Chem Eng J 302:137–145. CrossRefGoogle Scholar
  58. Xu LJ, Wang JL (2012) Fenton-like degradation of 2,4-dichlorophenol using Fe3O4 magnetic nanoparticles. Appl Catal B 123-124:117–126. CrossRefGoogle Scholar
  59. Yang L, Hu C, Nie Y, Qu J (2010) Surface acidity and reactivity of β-FeOOH/Al2O3 for pharmaceuticals degradation with ozone: in situ ATR-FTIR studies. Appl Catal B Environ 97(3-4):340–346. CrossRefGoogle Scholar
  60. Zhou T, Wu X, Zhang Y, Li J, Lim T (2013) Synergistic catalytic degradation of antibiotic sulfamethazine in a heterogeneous sonophotolytic goethite/oxalate Fenton-like system. Appl Catal B Environ 136-137:294–301. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Collaborative Innovation Center for Advanced Nuclear Energy Technology, INETTsinghua UniversityBeijingPeople’s Republic of China
  2. 2.School of Water Resources and EnvironmentChina University of GeosciencesBeijingChina
  3. 3.Beijing Key Laboratory of Radioactive Waste Treatment, INETTsinghua UniversityBeijingPeople’s Republic of China

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