Environmental Science and Pollution Research

, Volume 26, Issue 5, pp 4180–4191 | Cite as

Phosphorous-doped TiO2 nanoparticles: synthesis, characterization, and visible photocatalytic evaluation on sulfamethazine degradation

  • Sandra Yadira Mendiola-Alvarez
  • Ma. Aracely Hernández-Ramírez
  • Jorge Luis Guzmán-Mar
  • Lorena Leticia Garza-Tovar
  • Laura Hinojosa-ReyesEmail author
Advanced Oxidation Technologies: State-of-the-Art in Ibero-American Countries


Mesoporous phosphorous-doped TiO2 (TP) with different wt% of P (0.5, 1.0, and 1.5) was synthetized by microwave-assisted sol–gel method. The obtained materials were characterized by XRD with cell parameters refinement approach, Raman, BET-specific surface area analysis, SEM, ICP-OES, UV–Vis with diffuse reflectance, photoluminescence, FTIR, and XPS. The photocatalytic activity under visible light was evaluated on the degradation of sulfamethazine (SMTZ) at pH 8. The characterization of the phosphorous materials (TP) showed that incorporation of P in the lattice of TiO2 stabilizes the anatase crystalline phase, even increasing the annealing temperature. The mesoporous P-doped materials showed higher surface area and lower average crystallite size, band gap, and particle size; besides, more intense bands attributed to O–H bond were observed by FTIR analysis compared with bare TiO2. The P was substitutionally incorporated in the TiO2 lattice network as P5+ replacing Ti4+ to form Ti–O–P bonds and additionally present as PO43− on the TiO2 surface. All these characteristics explain the observed superior photocatalytic activity on degradation (100%) and mineralization (32%) of SMTZ under visible radiation by TP catalysts, especially for P-doped TiO2 1.0 wt% calcined at 450 °C (TP1.0-450). Ammonium, nitrate, and sulfate ions released during the photocatalytic degradation were quantified by ion chromatography; the nitrogen and sulfur mass balance evidenced the partial mineralization of this recalcitrant molecule.


Phosphorous-doped TiO2 Mesoporous material Heterogeneous photocatalysis Visible light Sulfamethazine Microwave-assisted sol–gel method 



Mendiola-Alvarez thanks the CONACYT for her doctorate scholarship.

Funding information

The authors gratefully acknowledge financial support from PAICYT UANL and Facultad de Ciencias Químicas, UANL.

Supplementary material

11356_2018_2314_MOESM1_ESM.docx (455 kb)
ESM 1 (DOCX 454 kb)


  1. Akpan U, Hameed B (2009) Parameters affecting the photocatalytic degradation of dyes using TiO2-based photocatalysts: a review. J Hazard Mater 170:520–529. CrossRefGoogle Scholar
  2. Ansari S, Cho M (2016) Highly visible light responsive, narrow band gap TiO2 nanoparticles modified by elemental red phosphorus for photocatalysis and photoelectrochemical applications. Sci Rep 6:1–10. CrossRefGoogle Scholar
  3. Babić S, Zrnčić M, Ljubas D (2015) Photolytic and thin TiO2 film assisted photocatalytic degradation of sulfamethazine in aqueous solution. Environ Sci Pollut Res 22:11372–11386. CrossRefGoogle Scholar
  4. Bahadur S, Bera S, Lee D (2013) Design of visible-light photocatalysts by coupling of narrow bandgap semiconductors and TiO2: effect of their relative energy band positions on the photocatalytic efficiency. Catal Sci Technol 3:1822–1830. CrossRefGoogle Scholar
  5. Batt A, Snow D, Aga D (2006) Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 64:1963–1971. CrossRefGoogle Scholar
  6. Ben W, Qiang Z, Yin X (2014) Adsorption behavior of sulfamethazine in an activated sludge process treating swine wastewater. J Environ Sci 26:1623–1629. CrossRefGoogle Scholar
  7. Cervantes M (2012) Diseño y síntesis de materiales a “medida” mediante el método sol-gel, UNEDGoogle Scholar
  8. Chen J, Shunchen Q, Yuexiang Z, Youchang X (2011) Phosphorous-modified TiO2 with excellent thermal stability and its application to the degradation of pollutants in water. Chin J Catal 32:1173–1179. CrossRefGoogle Scholar
  9. Devi L, Kavitha R (2013) A review on non metal ion doped titania for the photocatalytic degradation of organic pollutants under UV/solar light: role of photogenerated charge carrier dynamics in enhancing the activity. Appl Catal B Environ 140–141:559–587. CrossRefGoogle Scholar
  10. Elghniji K, Soro J, Rossignol S, Ksibi M (2012) A simple route for the preparation of P-modified TiO2: effect of phosphorus on thermal stability and photocatalytic activity. J Taiwan Inst Chem Eng 43:132–139. CrossRefGoogle Scholar
  11. Ermokhina N, Nevinskiy V, Manorik P (2013) Synthesis and characterization of thermally stable large-pore mesoporous nanocrystalline anatase. J Solid State Chem 200:90–98. CrossRefGoogle Scholar
  12. Fan Y, Ji Y, Kong D (2015) Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process. J Hazard Mater 300:39–47. CrossRefGoogle Scholar
  13. García M, Villagrasa M, Díaz M, Barceló D (2010) LC-QqLIT MS analysis of nine sulfonamides and one of their acetylated metabolites in the Llobregat River basin. Quantitative determination and qualitative evaluation by IDA experiments. Anal Bioanal Chem 397:1325–1334. CrossRefGoogle Scholar
  14. Gopal N, Lo H, Ke T (2012) Visible light active phosphorus-doped TiO2 nanoparticles: an EPR evidence for the enhanced charge separation. J Phys Chem C 116:16191–16197. CrossRefGoogle Scholar
  15. Guo S, Wang F, Sun J (2010) Marked enhancement of photocatalytic activity of P-doped TiO2 with hydrothermal method. Adv Mater Res 113–116:2150–2215. CrossRefGoogle Scholar
  16. Guo C, Xu J, Wang S (2013) Photodegradation of sulfamethazine in an aqueous solution by a bismuth molybdate photocatalyst. Catal Sci Technol 3:160. CrossRefGoogle Scholar
  17. Hsuan-Fu Y (2007) Photocatalytic abilities of gel-derived P-doped TiO2. J Phys Chem Solids 68:600–607. CrossRefGoogle Scholar
  18. Iwase M, Yamada K, Kurisaki T (2013a) A study on the active sites for visible-light photocatalytic activity of phosphorus-doped titanium (IV) oxide particles prepared using a phosphide compound. Appl Catal B Environ 141:327–332CrossRefGoogle Scholar
  19. Iwase M, Yamada K, Kurisaki T (2013b) Visible-light photocatalysis with phosphorus-doped titanium (IV) oxide particles prepared using a phosphide compound. Appl Catal B Environ 132–133:39–34. CrossRefGoogle Scholar
  20. Kaniou S, Pitarakis K, Barlagianni I, Poulios I (2005) Photocatalytic oxidation of sulfamethazine. Chemosphere 60:372–380. CrossRefGoogle Scholar
  21. Kesong Y, Ying D, Baibiao H (2007) Understanding photocatalytic activity of S- and P-doped TiO2 under visible light from first-principles. J Phys Chem C 51:18985–18994Google Scholar
  22. Körösi L, Papp S, Bertóti I, Dékány I (2007) Surface and bulk composition, structure, and photocatalytic activity of phosphate-modified TiO2. Chem Mater 19:4811–4819. CrossRefGoogle Scholar
  23. Kuo C, Wu C, Wu J, Chen Y (2015) Synthesis and characterization of a phosphorus-doped TiO2 immobilized bed for the photodegradation of bisphenol A under UV and sunlight irradiation. React Kinet Mech Catal 114:753–766. CrossRefGoogle Scholar
  24. Lertpaitoonpan W, Ong S, Moorman T (2009) Effect of organic carbon and pH on soil sorption of sulfamethazine. Chemosphere 76:558–564. CrossRefGoogle Scholar
  25. Li F, Jiang Y, Xia M (2009) Effect of the P/Ti ratio on the visible-light photocatalytic activity of P-doped TiO2. J Phys Chem 113:18134–18141Google Scholar
  26. Lin L, Zheng R, Xie J (2007) Synthesis and characterization of phosphor and nitrogen co-doped titania. Appl Catal B Environ 76:196–202. CrossRefGoogle Scholar
  27. Liu Y, Wang J (2013) Degradation of sulfamethazine by gamma irradiation in the presence of hydrogen peroxide. J Hazard Mater 250–251:99–105. CrossRefGoogle Scholar
  28. Lv Y, Yu L, Huang H (2009) Preparation, characterization of P-doped TiO2 nanoparticles and their excellent photocatalystic properties under the solar light irradiation. J Alloys Compd 488:314–319. CrossRefGoogle Scholar
  29. Ma L, Jia I, Guo X, Xiang L (2014) Current status and perspective of rare earth catalytic materials and catalysis. Chin J Catal 35:108–119. CrossRefGoogle Scholar
  30. Martinez J (2009) Environmental pollution by antibiotics and by antibiotic resistance determinants. Environ Pollut 157:2893–2902. CrossRefGoogle Scholar
  31. Mendiola S, Guzmán J, Turnes G, Maya A, Hernández A, Hinojosa L (2017) UV and visible activation of Cr(III)-doped TiO2 catalyst prepared by a microwave-assisted sol–gel method during MCPA degradation. Environ Sci Pollut Res 24:12673–12682. CrossRefGoogle Scholar
  32. Miranda N, Suárez S, Maldonado M (2014) Regeneration approaches for TiO2 immobilized photocatalyst used in the elimination of emerging contaminants in water. Catal Today 230:27–34. CrossRefGoogle Scholar
  33. Mohamed R, Aazam E (2013) Synthesis and characterization of P-doped TiO2 thin-films for photocatalytic degradation of butyl benzyl phthalate under visible-light irradiation. Chin J Catal 34:1267–1273. CrossRefGoogle Scholar
  34. Niu J, Lu P, Kang M (2014) P-doped TiO2 with superior visible-light activity prepared by rapid microwave hydrothermal method. Appl Surf Sci 319:99–106. CrossRefGoogle Scholar
  35. Shi Q, Yang D, Jiang Z, Li J (2006) Visible-light photocatalytic regeneration of NADH using P-doped TiO2 nanoparticles. J Mol Catal B Enzym 43:44–48. CrossRefGoogle Scholar
  36. Sotelo C, Noor N, Kafizas A (2015) Multifunctional P-doped TiO2 films: a new approach to self-cleaning, transparent conducting oxide materials. Chem Mater 27:3234–3242. CrossRefGoogle Scholar
  37. Tongon W, Chawengkijwanich C, Chiarakorn S (2014) Visible light responsive Ag/TiO2/MCM-41 nanocomposite films synthesized by a microwave assisted sol-gel technique. Superlattice Microst 69:108–121. CrossRefGoogle Scholar
  38. Tzeng T, Wang S, Chen C (2016) Photolysis and photocatalytic decomposition of sulfamethazine antibiotics in an aqueous solution with TiO2. RSC Adv 6:69301–69310. CrossRefGoogle Scholar
  39. Wang S, Zhou S (2011) Photodegradation of methyl orange by photocatalyst of CNTs/P-TiO2 under UV and visible-light irradiation. J Hazard Mater 185:77–85. CrossRefGoogle Scholar
  40. Xia Y, Jiang Y, Li F (2014) Effect of calcined atmosphere on the photocatalytic activity of P-doped TiO2. Appl Surf Sci 289:306–315. CrossRefGoogle Scholar
  41. Yap P, Cheah Y, Srinivasan M, Lim T (2012) Bimodal N-doped P25-TiO2/AC composite: preparation, characterization, physical stability, and synergistic adsorptive-solar photocatalytic removal of sulfamethazine. Appl Catal A Gen 427–428:125–136. CrossRefGoogle Scholar
  42. Yu J, Zhang L, Zheng Z, Zhao J (2003) Synthesis and characterization of phosphated mesoporous titanium dioxide with high photocatalytic activity. Chem Mater 15:2280–2286. CrossRefGoogle Scholar
  43. Yu J, Xiang Q, Zhou M (2009) Preparation, characterization and visible-light-driven photocatalytic activity of Fe-doped titania nanorods and first-principles study for electronic structures. Appl Catal B Environ 90:595–602. CrossRefGoogle Scholar
  44. Zhang Y, Fu W, Yang H (2009) Synthesis and characterization of P-doped TiO2 nanotubes. 518:99–103.
  45. Zhao D, Chen C, Wang Y (2008) Surface modification of TiO2 by phosphate: effect on photocatalytic activity and mechanism implication. J Phys Chem C 112:5993–6001. CrossRefGoogle Scholar
  46. Zhu Y, Zheng R, Lin L (2008) State of phosphor and its influence on the physicochemical and photocatalytic properties of P-doped titania. J Phys Chem C 112:15502–15509CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Facultad de Ciencias Químicas, Cd. UniversitariaUniversidad Autónoma de Nuevo León, UANLSan Nicolás de los GarzaMéxico

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