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TiO2-catalyzed photodegradation of aromatic compounds: relevance of susceptibility to oxidation and electrophilic attack by hydroxyl radical

  • Fabiola Cristina Ricci Spazzini
  • Thomaz Pol Ximenes
  • Valdecir Farias Ximenes
Research Paper
  • 31 Downloads

Abstract

The application of nanostructured titanium dioxide (TiO2) as catalyst for the photodegradation of drugs and dyes is well established. We aimed to evaluate the importance of the reactivity of aromatic compounds submitted to photodegradation. Specifically, we were interested in the correlation between susceptibility to oxidation and/or to electrophilic attack and the efficiency of degradation. We demonstrated that hydroxyl radical (HO˙) is the most relevant species generated in the photodegradation process. Considering that HO˙ has both oxidizing and electrophilic features, the efficiency of degradation of selected aromatic compounds was performed. The choice was based on their susceptibility to oxidation and/or to electrophilic attack. Benzoic acid (C1), salicylic acid (C2), and protocatechuic acid (C3) were compared regarding their oxidability using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay and were ranked as follows: C3 ≫ C2~C1. These compounds were efficiently photodegraded and no significant difference was observed among them. To assess the importance of susceptibility to electrophilic attack, anisole (C4), acetophenone (C5), and nitrobenzene (C6) were selected. Compared to C5 and C6, the higher susceptibility of C4 to electrophilic attack was demonstrated using hypochlorous acid, an electrophilic reagent. The photodegradation showed that C4 was also more susceptible to degradation compared to C5 and C6. In summary, we found that by acting as a powerful oxidant/electrophile agent, HO˙ was able to promote the degradation of aromatic moieties. Considering that the majority of drugs and dyes bear aromatic moieties, our findings explain the great success of photodegradation using metal oxides as catalysts.

Keywords

Titanium dioxide Photodegradation Aromatic compounds Pharmaceutical drugs Electrophilic susceptibility Nanostructured catalysts 

Notes

Funding information

This work was supported by grants from the São Paulo Research Foundation (FAPESP, #2016/20549-5), National Council for Scientific and Technological Development (CNPq #302793/2016-0), and Coordination for the improvement of higher education (CAPES).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4433_MOESM1_ESM.docx (219 kb)
ESM 1 (DOCX 219 kb)

References

  1. Addamo M, Augugliaro V, Coluccia S, Paola AD, García-López E, Loddo V, Marcì G, Martra G, Palmisano L (2006) The role of water in the photocatalytic degradation of acetonitrile and toluene in gas-solid and liquid-solid regimes. Int J Photoenergy 2006:1–12.  https://doi.org/10.1155/IJP/2006/39182 CrossRefGoogle Scholar
  2. Atkinson R (1988) Estimation of gas-phase hydroxyl radical rate constants for organic chemicals. Environ Toxicol Chem 7:435–442.  https://doi.org/10.1002/etc.5620070604 CrossRefGoogle Scholar
  3. Aulakh MK, Arora N, Kumar A, Ali A, Pal B (2017) Effect of different shapes of TiO2 nanoparticles on the catalytic photodegradation of salicylic acid under UV light. J Nanosci Nanotechnol 17:5303–5309.  https://doi.org/10.1166/jnn.2017.13851 CrossRefGoogle Scholar
  4. Awfa D, Ateia M, Fujii M, Johnson MS, Yoshimura C (2018) Photodegradation of pharmaceuticals and personal care products in water treatment using carbonaceous-TiO 2 composites: a critical review of recent literature. Water Res 142:26–45.  https://doi.org/10.1016/j.watres.2018.05.036 CrossRefGoogle Scholar
  5. Brooms TJ, Onyango MS, Ochieng A (2017) Photodegradation of phenol using TiO2, ZnO and TiO2/ZnO catalysts in an annular reactor. J Water Chem Technol 39:155–160.  https://doi.org/10.3103/S1063455X17030067 CrossRefGoogle Scholar
  6. Carr SA, Baeza-Romero MT, Blitz MA, Price BJS, Seakins PW (2008) Ketone photolysis in the presence of oxygen: a useful source of OH for flash photolysis kinetics experiments. In J Chem Kinet 40:504–514.  https://doi.org/10.1002/kin.20330 CrossRefGoogle Scholar
  7. Chen Z, Yu X, Huang X, Zhang S (2014) Prediction of reaction rate of hydroxyl radical with organic compounds. J Chil Chem Soc 59:2252–2259.  https://doi.org/10.4067/S0717-97072014000100003 CrossRefGoogle Scholar
  8. Chen Y, Zhang X, Mao L, Yang Z (2017) Dependence of kinetics and pathway of acetaminophen photocatalytic degradation on irradiation photon energy and TiO 2 crystalline. Chem Eng J 330:1091–1099.  https://doi.org/10.1016/j.cej.2017.07.148 CrossRefGoogle Scholar
  9. Da Costa M, Ximenes VF, Da Fonseca LM (2004) Hypochlorous acid inhibition by acetoacetate: implications on neutrophil functions. Biol Pharm Bull 27:1183–1187.  https://doi.org/10.1248/bpb.27.1183 CrossRefGoogle Scholar
  10. Di Paola A, Bellardita M, Palmisano L (2013) Brookite, the least known TiO2 photocatalyst. Catalysts 3:36–73.  https://doi.org/10.3390/catal3010036 CrossRefGoogle Scholar
  11. Glorieux C, Calderon PB (2017) Catalase, a remarkable enzyme: targeting the oldest antioxidant enzyme to find a new cancer treatment approach. Biol Chem 398:1095–1108.  https://doi.org/10.1515/hsz-2017-0131 CrossRefGoogle Scholar
  12. Grabowska E, Reszczyńska J, Zaleska A (2012) RETRACTED: mechanism of phenol photodegradation in the presence of pure and modified-TiO 2 : a review. Water Res 46:5453–5471.  https://doi.org/10.1016/j.watres.2012.07.048 CrossRefGoogle Scholar
  13. Landsman NA, Swancutt KL, Bradford CN, Cox CR, Kiddle JJ, Mezyk SP (2007) Free radical chemistry of advanced oxidation process removal of nitrosamines in water. Environ Sci Technol 41:5818–5823CrossRefGoogle Scholar
  14. Liu S, Zhou X, Han W, Li J, Sun X, Shen J, Wang L (2017) Theoretical and experimental insights into the ·OH-mediated mineralization mechanism of flutriafol. Electrochim Acta 235:223–232.  https://doi.org/10.1016/j.electacta.2017.03.062 CrossRefGoogle Scholar
  15. Marusawa H, Ichikawa K, Narita N, Murakami H, Ito K, Tezuka T (2002) Hydroxyl radical as a strong electrophilic species. Bioorg Med Chem 10:2283–2290CrossRefGoogle Scholar
  16. Mehrvar M, Anderson WA, Moo-Young M (2000) Photocatalytic degradation of aqueous tetrahydrofuran, 1,4-dioxane, and their mixture with TiO 2. Int J Photoenergy 2:67–80.  https://doi.org/10.1155/S1110662X00000106 CrossRefGoogle Scholar
  17. Minakata D, Li K, Westerhoff P, Crittenden J (2009) Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants. Environ Sci Technol 43:6220–6227CrossRefGoogle Scholar
  18. Muhd Julkapli N, Bagheri S, Bee Abd Hamid S (2014) Recent advances in heterogeneous photocatalytic decolorization of synthetic dyes. Sci World J 2014:1–25.  https://doi.org/10.1155/2014/692307 CrossRefGoogle Scholar
  19. Ohara A, Miyamoto S (2012) Oxygen radicals and related species. In: Pantopoulos K, Schipper HM (eds) Principles of free radical biomedicine, vol. 1. Nova biomedical books, pp 19–42Google Scholar
  20. Olama N, Dehghani M, Malakootian M (2018) The removal of amoxicillin from aquatic solutions using the TiO2/UV-C nanophotocatalytic method doped with trivalent iron. Appl Water Sci 8:97.  https://doi.org/10.1007/s13201-018-0733-7 CrossRefGoogle Scholar
  21. Rochkind M, Pasternak S, Paz Y (2014) Using dyes for evaluating photocatalytic properties: a critical review. Molecules 20:88–110.  https://doi.org/10.3390/molecules20010088 CrossRefGoogle Scholar
  22. Sadrieyeh S, Malekfar R (2018) Photocatalytic performance of plasmonic Au/Ag-TiO 2 aerogel nanocomposites. J Non-Cryst Solids 489:33–39.  https://doi.org/10.1016/j.jnoncrysol.2018.03.020 CrossRefGoogle Scholar
  23. Sampaio MJ, Silva CG, Silva AMT, Vilar VJP, Boaventura RAR, Faria JL (2013) Photocatalytic activity of TiO2-coated glass raschig rings on the degradation of phenolic derivatives under simulated solar light irradiation. Chem Eng J 224:32–38.  https://doi.org/10.1016/j.cej.2012.11.027 CrossRefGoogle Scholar
  24. Simić A, Manojlović D, Segan D, Todorović M (2007) Electrochemical behavior and antioxidant and prooxidant activity of natural phenolics. Molecules 12:2327–2340CrossRefGoogle Scholar
  25. Singh P, Ojha A, Borthakur A, Singh R, Lahiry D, Tiwary D, Mishra PK (2016) Emerging trends in photodegradation of petrochemical wastes: a review. Environ Sci Pollut Res Int 23:22340–22364.  https://doi.org/10.1007/s11356-016-7373-y CrossRefGoogle Scholar
  26. Sviatenko L, Sviatenko LK, Gorb L et al (2016) Radical decomposition of 2,4-dinitrotoluene (DNT) at conditions of advanced oxidation. Computational study. Bull Dnipropetr Natl Univ Ser Chem 24:56–61.  https://doi.org/10.15421/081608 CrossRefGoogle Scholar
  27. Tekin G, Ersöz G, Atalay S (2018) Degradation of benzoic acid by advanced oxidation processes in the presence of Fe or Fe-TiO 2 loaded activated carbon derived from walnut shells: a comparative study. J Environ Chem Eng 6:1745–1759.  https://doi.org/10.1016/j.jece.2018.01.067 CrossRefGoogle Scholar
  28. Tong A, Braund R, Warren D, Peake B (2012) TiO2-assisted photodegradation of pharmaceuticals — a review. Open Chem 10:989–1027.  https://doi.org/10.2478/s11532-012-0049-7 CrossRefGoogle Scholar
  29. Trawiński J, Skibiński R, Szymański P (2018) Investigation of the photolysis and TiO 2 , SrTiO 3 , H 2 O 2 -mediated photocatalysis of an antipsychotic drug loxapine – evaluation of kinetics, identification of photoproducts, and in silico estimation of properties. Chemosphere 204:1–10.  https://doi.org/10.1016/j.chemosphere.2018.04.022 CrossRefGoogle Scholar
  30. Ullattil SG, Narendranath SB, Pillai SC, Periyat P (2018) Black TiO 2 nanomaterials: a review of recent advances. Chem Eng J 343:708–736.  https://doi.org/10.1016/j.cej.2018.01.069 CrossRefGoogle Scholar
  31. Vilhunen S, Puton J, Virkutyte J, Sillanpää M (2011) Efficiency of hydroxyl radical formation and phenol decomposition using UV light emitting diodes and H 2 O 2. Environ Technol 32:865–872.  https://doi.org/10.1080/09593330.2010.516770 CrossRefGoogle Scholar
  32. Wolf VG, Bonacorsi C, Raddi MSG, da Fonseca LM, Ximenes VF (2017) Octyl gallate, a food additive with potential beneficial properties to treat: Helicobacter pylori infection. Food Funct 8:2500–2511.  https://doi.org/10.1039/c7fo00707h CrossRefGoogle Scholar
  33. Xian T, Yang H, Di L et al (2014) Photocatalytic reduction synthesis of SrTiO3-graphene nanocomposites and their enhanced photocatalytic activity. Nanoscale Res Lett 9:327.  https://doi.org/10.1186/1556-276X-9-327 CrossRefGoogle Scholar
  34. Xian T, Yang H, Huo YS, Ma JY, Zhang HM, Su JY, Feng WJ (2016) Fabrication of ag-decorated CaTiO3 nanoparticles and their enhanced photocatalytic activity for dye degradation. J Nanosci Nanotechnol 16:570–575CrossRefGoogle Scholar
  35. Ximenes VF, Morgon NH, De Souza AR (2015) Hypobromous acid, a powerful endogenous electrophile: experimental and theoretical studies. J Inorg Biochem 146:61–68.  https://doi.org/10.1016/j.jinorgbio.2015.02.014 CrossRefGoogle Scholar
  36. Yang Z, Su R, Luo S, Spinney R, Cai M, Xiao R, Wei Z (2017) Comparison of the reactivity of ibuprofen with sulfate and hydroxyl radicals: an experimental and theoretical study. Sci Total Environ 590–591:751–760.  https://doi.org/10.1016/j.scitotenv.2017.03.039 CrossRefGoogle Scholar
  37. Youssef Z, Colombeau L, Yesmurzayeva N, Baros F, Vanderesse R, Hamieh T, Toufaily J, Frochot C, Roques-Carmes T, Acherar S (2018) Dye-sensitized nanoparticles for heterogeneous photocatalysis: cases studies with TiO 2, ZnO, fullerene and graphene for water purification. Dyes Pigments 159:49–71.  https://doi.org/10.1016/j.dyepig.2018.06.002 CrossRefGoogle Scholar
  38. Yuzawa H, Aoki M, Otake K, Hattori T, Itoh H, Yoshida H (2012) Reaction mechanism of aromatic ring hydroxylation by water over platinum-loaded titanium oxide photocatalyst. J Phys Chem C 116:25376–25387.  https://doi.org/10.1021/jp308453d CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of SciencesUNESP - São Paulo State UniversitySão PauloBrazil

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