Phosphorous-doped TiO 2 nanoparticles: synthesis, characterization, and visible photocatalytic evaluation on sulfamethazine degradation Advanced Oxidation Technologies: State-of-the-Art in Ibero-American Countries First Online: 24 May 2018 Abstract
Mesoporous phosphorous-doped TiO
2 (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 TiO 2 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 TiO 2. The P was substitutionally incorporated in the TiO 2 lattice network as P 5+ replacing Ti 4+ to form Ti–O–P bonds and additionally present as PO 4 3− on the TiO 2 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 TiO 2 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. Keywords Phosphorous-doped TiO 2 Mesoporous material Heterogeneous photocatalysis Visible light Sulfamethazine Microwave-assisted sol–gel method
Responsible editor: Suresh Pillai
Electronic supplementary material
The online version of this article (
) contains supplementary material, which is available to authorized users. https://doi.org/10.1007/s11356-018-2314-6 Notes Acknowledgements
Mendiola-Alvarez thanks the CONACYT for her doctorate scholarship.
The authors gratefully acknowledge financial support from PAICYT UANL and Facultad de Ciencias Químicas, UANL.
Akpan U, Hameed B (2009) Parameters affecting the photocatalytic degradation of dyes using TiO
-based photocatalysts: a review. J Hazard Mater 170:520–529.
https://doi.org/10.1016/j.jhazmat.2009.05.039 CrossRef Google Scholar
Ansari S, Cho M (2016) Highly visible light responsive, narrow band gap TiO
nanoparticles modified by elemental red phosphorus for photocatalysis and photoelectrochemical applications. Sci Rep 6:1–10.
https://doi.org/10.1038/srep25405 CrossRef Google Scholar
Babić S, Zrnčić M, Ljubas D (2015) Photolytic and thin TiO
film assisted photocatalytic degradation of sulfamethazine in aqueous solution. Environ Sci Pollut Res 22:11372–11386.
https://doi.org/10.1007/s11356-015-4338-5 CrossRef Google Scholar
Bahadur S, Bera S, Lee D (2013) Design of visible-light photocatalysts by coupling of narrow bandgap semiconductors and TiO
: effect of their relative energy band positions on the photocatalytic efficiency. Catal Sci Technol 3:1822–1830.
https://doi.org/10.1039/c3cy00004d CrossRef Google Scholar
Batt A, Snow D, Aga D (2006) Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 64:1963–1971.
https://doi.org/10.1016/j.chemosphere.2006.01.029 CrossRef Google Scholar
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.
https://doi.org/10.1016/j.jes.2014.06.002 CrossRef Google Scholar
Cervantes M (2012) Diseño y síntesis de materiales a “medida” mediante el método sol-gel, UNED
Chen J, Shunchen Q, Yuexiang Z, Youchang X (2011) Phosphorous-modified TiO
with excellent thermal stability and its application to the degradation of pollutants in water. Chin J Catal 32:1173–1179.
https://doi.org/10.1016/S1872-2067(10)60229-X CrossRef Google Scholar
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.
https://doi.org/10.1016/j.apcatb.2013.04.035 CrossRef Google Scholar
Elghniji K, Soro J, Rossignol S, Ksibi M (2012) A simple route for the preparation of P-modified TiO
: effect of phosphorus on thermal stability and photocatalytic activity. J Taiwan Inst Chem Eng 43:132–139.
https://doi.org/10.1016/j.jtice.2011.06.011 CrossRef Google Scholar
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.
https://doi.org/10.1016/j.jssc.2012.12.034 CrossRef Google Scholar
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.
https://doi.org/10.1016/j.jhazmat.2015.06.058 CrossRef Google Scholar
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.
https://doi.org/10.1007/s00216-010-3630-y CrossRef Google Scholar
Gopal N, Lo H, Ke T (2012) Visible light active phosphorus-doped TiO
nanoparticles: an EPR evidence for the enhanced charge separation. J Phys Chem C 116:16191–16197.
https://doi.org/10.1021/jp212346f CrossRef Google Scholar
Guo S, Wang F, Sun J (2010) Marked enhancement of photocatalytic activity of P-doped TiO
with hydrothermal method. Adv Mater Res 113–116:2150–2215.
https://doi.org/10.4028/www.scientific.net/AMR.113-116.2150 CrossRef Google Scholar
Guo C, Xu J, Wang S (2013) Photodegradation of sulfamethazine in an aqueous solution by a bismuth molybdate photocatalyst. Catal Sci Technol 3:160.
https://doi.org/10.1039/c3cy20811g CrossRef Google Scholar
Hsuan-Fu Y (2007) Photocatalytic abilities of gel-derived P-doped TiO
. J Phys Chem Solids 68:600–607.
https://doi.org/10.1016/j.jpcs.2007.01.050 CrossRef Google Scholar
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 141:327–332
CrossRef Google Scholar
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.
https://doi.org/10.1016/j.apcatb.2012.11.014 CrossRef Google Scholar
Kaniou S, Pitarakis K, Barlagianni I, Poulios I (2005) Photocatalytic oxidation of sulfamethazine. Chemosphere 60:372–380.
https://doi.org/10.1016/j.chemosphere.2004.11.069 CrossRef Google Scholar
Kesong Y, Ying D, Baibiao H (2007) Understanding photocatalytic activity of S- and P-doped TiO
under visible light from first-principles. J Phys Chem C 51:18985–18994
Körösi L, Papp S, Bertóti I, Dékány I (2007) Surface and bulk composition, structure, and photocatalytic activity of phosphate-modified TiO
. Chem Mater 19:4811–4819.
https://doi.org/10.1021/cm070692r CrossRef Google Scholar
Kuo C, Wu C, Wu J, Chen Y (2015) Synthesis and characterization of a phosphorus-doped TiO
immobilized bed for the photodegradation of bisphenol A under UV and sunlight irradiation. React Kinet Mech Catal 114:753–766.
https://doi.org/10.1007/s11144-014-0783-2 CrossRef Google Scholar
Lertpaitoonpan W, Ong S, Moorman T (2009) Effect of organic carbon and pH on soil sorption of sulfamethazine. Chemosphere 76:558–564.
https://doi.org/10.1016/j.chemosphere.2009.02.066 CrossRef Google Scholar
Li F, Jiang Y, Xia M (2009) Effect of the P/Ti ratio on the visible-light photocatalytic activity of P-doped TiO
. J Phys Chem 113:18134–18141
Lin L, Zheng R, Xie J (2007) Synthesis and characterization of phosphor and nitrogen co-doped titania. Appl Catal B Environ 76:196–202.
https://doi.org/10.1016/j.apcatb.2007.05.023 CrossRef Google Scholar
Liu Y, Wang J (2013) Degradation of sulfamethazine by gamma irradiation in the presence of hydrogen peroxide. J Hazard Mater 250–251:99–105.
https://doi.org/10.1016/j.jhazmat.2013.01.050 CrossRef Google Scholar
Lv Y, Yu L, Huang H (2009) Preparation, characterization of P-doped TiO
nanoparticles and their excellent photocatalystic properties under the solar light irradiation. J Alloys Compd 488:314–319.
https://doi.org/10.1016/j.jallcom.2009.08.116 CrossRef Google Scholar
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.
https://doi.org/10.1016/S1872 CrossRef Google Scholar
Martinez J (2009) Environmental pollution by antibiotics and by antibiotic resistance determinants. Environ Pollut 157:2893–2902.
https://doi.org/10.1016/j.envpol.2009.05.051 CrossRef Google Scholar
Mendiola S, Guzmán J, Turnes G, Maya A, Hernández A, Hinojosa L (2017) UV and visible activation of Cr(III)-doped TiO
catalyst prepared by a microwave-assisted sol–gel method during MCPA degradation. Environ Sci Pollut Res 24:12673–12682.
https://doi.org/10.1007/s11356-016-8034-x CrossRef Google Scholar
Miranda N, Suárez S, Maldonado M (2014) Regeneration approaches for TiO
immobilized photocatalyst used in the elimination of emerging contaminants in water. Catal Today 230:27–34.
https://doi.org/10.1016/j.cattod.2013.12.048 CrossRef Google Scholar
Mohamed R, Aazam E (2013) Synthesis and characterization of P-doped TiO
thin-films for photocatalytic degradation of butyl benzyl phthalate under visible-light irradiation. Chin J Catal 34:1267–1273.
https://doi.org/10.1016/S1872-2067(12)60572-5 CrossRef Google Scholar
Niu J, Lu P, Kang M (2014) P-doped TiO
with superior visible-light activity prepared by rapid microwave hydrothermal method. Appl Surf Sci 319:99–106.
https://doi.org/10.1016/j.apsusc.2014.07.048 CrossRef Google Scholar
Shi Q, Yang D, Jiang Z, Li J (2006) Visible-light photocatalytic regeneration of NADH using P-doped TiO
nanoparticles. J Mol Catal B Enzym 43:44–48.
https://doi.org/10.1016/j.molcatb.2006.06.005 CrossRef Google Scholar
Sotelo C, Noor N, Kafizas A (2015) Multifunctional P-doped TiO
films: a new approach to self-cleaning, transparent conducting oxide materials. Chem Mater 27:3234–3242.
https://doi.org/10.1021/cm504734a CrossRef Google Scholar
Tongon W, Chawengkijwanich C, Chiarakorn S (2014) Visible light responsive Ag/TiO
/MCM-41 nanocomposite films synthesized by a microwave assisted sol-gel technique. Superlattice Microst 69:108–121.
https://doi.org/10.1016/j.spmi.2014.02.003 CrossRef Google Scholar
Tzeng T, Wang S, Chen C (2016) Photolysis and photocatalytic decomposition of sulfamethazine antibiotics in an aqueous solution with TiO
. RSC Adv 6:69301–69310.
https://doi.org/10.1039/C6RA13435A CrossRef Google Scholar
Wang S, Zhou S (2011) Photodegradation of methyl orange by photocatalyst of CNTs/P-TiO
under UV and visible-light irradiation. J Hazard Mater 185:77–85.
https://doi.org/10.1016/j.jhazmat.2010.08.125 CrossRef Google Scholar
Xia Y, Jiang Y, Li F (2014) Effect of calcined atmosphere on the photocatalytic activity of P-doped TiO
. Appl Surf Sci 289:306–315.
https://doi.org/10.1016/j.apsusc.2013.10.157 CrossRef Google Scholar
Yap P, Cheah Y, Srinivasan M, Lim T (2012) Bimodal N-doped P25-TiO
/AC composite: preparation, characterization, physical stability, and synergistic adsorptive-solar photocatalytic removal of sulfamethazine. Appl Catal A Gen 427–428:125–136.
https://doi.org/10.1016/j.apcata.2012.03.042 CrossRef Google Scholar
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.
https://doi.org/10.1021/cm0340781 CrossRef Google Scholar
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.
https://doi.org/10.1016/j.apcatb.2009.04.021 CrossRef Google Scholar
Zhang Y, Fu W, Yang H (2009) Synthesis and characterization of P-doped TiO
Zhao D, Chen C, Wang Y (2008) Surface modification of TiO
by phosphate: effect on photocatalytic activity and mechanism implication. J Phys Chem C 112:5993–6001.
https://doi.org/10.1021/jp712049c CrossRef Google Scholar
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 112:15502–15509
CrossRef Google Scholar Copyright information
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