Photocatalytic Degradation of Selected Pharmaceuticals Using g-C3N4 and TiO2 Nanomaterials
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials and Reagents
2.2. Preparation of Exfoliated g-C3N4
2.3. Materials Characterization
2.4. Photocatalytic Experiments and Analytical Methods
3. Results and Discussion
3.1. Diffusion Reflectance Spectrometry
3.2. X-ray Diffraction
3.3. FTIR-ATR Spectrometry
3.4. TEM Analysis and Specific Surface Area
3.5. Moisture Adsorption
3.6. Photocatalytic Degradation of Selected Pharmaceuticals
Evaluation of Photodegradation Kinetics
3.7. Photodegradation and Analysis of Intermediates
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Barbosa, M.O.; Moreira, N.F.F.; Ribeiro, A.R.; Pereira, M.F.R.; Silva, A.M.T. Occurrence and removal of organic micropollutants: An overview of the watch list of EU Decision 2015/495. Water Res. 2016, 94, 257–279. [Google Scholar] [CrossRef] [PubMed]
- Fekadu, S.; Alemayehu, E.; Dewil, R.; Van der Bruggen, B. Pharmaceuticals in freshwater aquatic environments: A comparison of the African and European challenge. Sci. Total Environ. 2019, 654, 324–337. [Google Scholar] [CrossRef] [PubMed]
- Manvendra, P.; Kumar, R.; Kishor, K.; Mlsna, T.; Pittman, C.U.; Mohan, D. Pharmaceuticals of Emerging Concern in Aquatic Systems: Chemistry, Occurrence, Effects, and Removal Methods. Chem. Rev. 2019, 119, 3510–3673. [Google Scholar] [CrossRef] [Green Version]
- Ojemaye, C.Y.; Petrik, L. Pharmaceuticals in the marine environment: A review. Environ. Rev. 2018, 27, 151–165. [Google Scholar] [CrossRef]
- Kim, M.-K.; Zoh, K.-D. Occurrence and removals of micropollutants in water environment. Environ. Eng. Res. 2016, 21, 319–332. [Google Scholar] [CrossRef] [Green Version]
- Yang, Y.; Ok, Y.S.; Kim, K.-H.; Kwon, E.E.; Tsang, Y.F. Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: A review. Sci. Total Environ. 2017, 596–597, 303–320. [Google Scholar] [CrossRef] [PubMed]
- Petrie, B.; Barden, R.; Kasprzyk-Hordern, B. A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring. Water Res. 2015, 72, 3–27. [Google Scholar] [CrossRef]
- Quesada, H.B.; Baptista, A.T.A.; Cusioli, L.F.; Seibert, D.; de Oliveira Bezerra, C.; Bergamasco, R. Surface water pollution by pharmaceuticals and an alternative of removal by low-cost adsorbents: A review. Chemosphere 2019, 222, 766–780. [Google Scholar] [CrossRef]
- Xu, Y.; Liu, T.; Zhang, Y.; Ge, F.; Steel, R.M.; Sun, L. Advances in technologies for pharmaceuticals and personal care products removal. J. Mater. Chem. A 2017, 5, 12001–12014. [Google Scholar] [CrossRef]
- Tiwari, B.; Sellamuthu, B.; Ouarda, Y.; Drogui, P.; Tyagi, R.D.; Buelna, G. Review on fate and mechanism of removal of pharmaceutical pollutants from wastewater using biological approach. Bioresour. Technol. 2017, 224, 1–12. [Google Scholar] [CrossRef] [Green Version]
- Kanakaraju, D.; Glass, B.D.; Oelgemöller, M. Advanced oxidation process-mediated removal of pharmaceuticals from water: A review. J. Environ. Manag. 2018, 219, 189–207. [Google Scholar] [CrossRef] [PubMed]
- Elisa, L.; Edgar, M.; Kim, M.B.; Saul, N.; Elvira, Z. A Review on Chemical Advanced Oxidation Processes for Pharmaceuticals with Paracetamol as a Model Compound. Reaction Conditions, Intermediates and Total Mechanism. Curr. Org. Chem. 2018, 22, 2–17. [Google Scholar] [CrossRef]
- Rivera-Utrilla, J.; Sánchez-Polo, M.; Ferro-García, M.Á.; Prados-Joya, G.; Ocampo-Pérez, R. Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere 2013, 93, 1268–1287. [Google Scholar] [CrossRef] [PubMed]
- Esplugas, S.; Bila, D.M.; Krause, L.G.T.; Dezotti, M. Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in water effluents. J. Hazard. Mater. 2007, 149, 631–642. [Google Scholar] [CrossRef] [PubMed]
- Kanakaraju, D.; Glass, B.; Oelgemöller, M. Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environ. Chem. Lett. 2014, 12, 27–47. [Google Scholar] [CrossRef]
- Awfa, D.; Ateia, M.; Fujii, M.; Johnson, M.S.; Yoshimura, C. Photodegradation of pharmaceuticals and personal care products in water treatment using carbonaceous-TiO2 composites: A critical review of recent literature. Water Res. 2018, 142, 26–45. [Google Scholar] [CrossRef] [PubMed]
- Durán, A.; Monteagudo, J.M.; San Martín, I. Operation costs of the solar photo-catalytic degradation of pharmaceuticals in water: A mini-review. Chemosphere 2018, 211, 482–488. [Google Scholar] [CrossRef]
- Sarkar, S.; Das, R.; Choi, H.; Bhattacharjee, C. Involvement of process parameters and various modes of application of TiO2 nanoparticles in heterogeneous photocatalysis of pharmaceutical wastes – a short review. RSC Adv. 2014, 4, 57250–57266. [Google Scholar] [CrossRef]
- Tong, A.; Braund, R.; Warren, D.; Peake, B. TiO2-assisted photodegradation of pharmaceuticals—A review. Open Chem. 2012, 10, 989. [Google Scholar] [CrossRef]
- Calza, P.; Sakkas, V.A.; Medana, C.; Baiocchi, C.; Dimou, A.; Pelizzetti, E.; Albanis, T. Photocatalytic degradation study of diclofenac over aqueous TiO2 suspensions. Appl. Catal. B 2006, 67, 197–205. [Google Scholar] [CrossRef]
- Martínez, C.; Canle, L.M.; Fernández, M.I.; Santaballa, J.A.; Faria, J. Aqueous degradation of diclofenac by heterogeneous photocatalysis using nanostructured materials. Appl. Catal. B 2011, 107, 110–118. [Google Scholar] [CrossRef]
- Rimoldi, L.; Meroni, D.; Falletta, E.; Ferretti, A.M.; Gervasini, A.; Cappelletti, G.; Ardizzone, S. The role played by different TiO2 features on the photocatalytic degradation of paracetamol. Appl. Surf. Sci. 2017, 424, 198–205. [Google Scholar] [CrossRef]
- Yang, L.; Yu, L.E.; Ray, M.B. Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis. Water Res. 2008, 42, 3480–3488. [Google Scholar] [CrossRef] [PubMed]
- Candido, J.P.; Andrade, S.J.; Fonseca, A.L.; Silva, F.S.; Silva, M.R.A.; Kondo, M.M. Ibuprofen removal by heterogeneous photocatalysis and ecotoxicological evaluation of the treated solutions. Environ. Sci. Pollut. Res. Int. 2016, 23, 19911–19920. [Google Scholar] [CrossRef] [PubMed]
- Choina, J.; Kosslick, H.; Fischer, C.; Flechsig, G.U.; Frunza, L.; Schulz, A. Photocatalytic decomposition of pharmaceutical ibuprofen pollutions in water over titania catalyst. Appl. Catal. B 2013, 129, 589–598. [Google Scholar] [CrossRef]
- Zhu, B.; Zhang, L.; Cheng, B.; Yu, J. First-principle calculation study of tri-s-triazine-based g-C3N4: A review. Appl. Catal. B 2018, 224, 983–999. [Google Scholar] [CrossRef]
- Zhou, Z.; Zhang, Y.; Shen, Y.; Liu, S.; Zhang, Y. Molecular engineering of polymeric carbon nitride: Advancing applications from photocatalysis to biosensing and more. Chem. Soc. Rev. 2018, 47, 2298–2321. [Google Scholar] [CrossRef] [PubMed]
- Wang, Y.; Wang, X.; Antonietti, M. Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: From photochemistry to multipurpose catalysis to sustainable chemistry. Angew. Chem. Int. Edit. 2012, 51, 68–89. [Google Scholar] [CrossRef]
- Ong, W.-J.; Tan, L.-L.; Ng, Y.H.; Yong, S.-T.; Chai, S.-P. Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability? Chem. Rev. 2016, 116, 7159–7329. [Google Scholar] [CrossRef]
- Cao, S.; Low, J.; Yu, J.; Jaroniec, M. Polymeric photocatalysts based on graphitic carbon nitride. Adv. Mater. 2015, 27, 2150–2176. [Google Scholar] [CrossRef]
- Moniz, S.J.A.; Shevlin, S.A.; Martin, D.J.; Guo, Z.-X.; Tang, J. Visible-light driven heterojunction photocatalysts for water splitting – a critical review. Energy Environ. Sci. 2015, 8, 731–759. [Google Scholar] [CrossRef]
- Zhao, Z.; Sun, Y.; Dong, F. Graphitic carbon nitride based nanocomposites: A review. Nanoscale 2015, 7, 15–37. [Google Scholar] [CrossRef] [PubMed]
- Svoboda, L.; Praus, P.; Lima, M.J.; Sampaio, M.J.; Matýsek, D.; Ritz, M.; Dvorský, R.; Faria, J.L.; Silva, C.G. Graphitic carbon nitride nanosheets as highly efficient photocatalysts for phenol degradation under high-power visible LED irradiation. Mater. Res. Bull. 2018, 100, 322–332. [Google Scholar] [CrossRef]
- Moreira, N.F.F.; Sampaio, M.J.; Ribeiro, A.R.; Silva, C.G.; Faria, J.L.; Silva, A.M.T. Metal-free g-C3N4 photocatalysis of organic micropollutants in urban wastewater under visible light. Appl. Catal. B 2019, 248, 184–192. [Google Scholar] [CrossRef]
- Hernández-Uresti, D.B.; Vázquez, A.; Sanchez-Martinez, D.; Obregón, S. Performance of the polymeric g-C3N4 photocatalyst through the degradation of pharmaceutical pollutants under UV–vis irradiation. J. Photochem. Photobiol. A 2016, 324, 47–52. [Google Scholar] [CrossRef]
- Castrejón-Sánchez, V.H.; López, R.; Ramón-González, M.; Enríquez-Pérez, Á.; Camacho-López, M.; Villa-Sánchez, G. Annealing Control on the Anatase/Rutile Ratio of Nanostructured Titanium Dioxide Obtained by Sol-Gel. Crystals 2018, 9, 22. [Google Scholar] [CrossRef]
- Halder, N.C.; Wagner, C.N.J. Separation of particle size and lattice strain in integral breadth measurements. Acta Crystallogr. 1966, 20, 312–313. [Google Scholar] [CrossRef]
- Fina, F.; Callear, S.K.; Carins, G.M.; Irvine, J.T.S. Structural Investigation of Graphitic Carbon Nitride via XRD and Neutron Diffraction. Chem. Mater. 2015, 27, 2612–2618. [Google Scholar] [CrossRef] [Green Version]
- Kakuma, Y.; Nosaka, A.Y.; Nosaka, Y. Difference in TiO2 photocatalytic mechanism between rutile and anatase studied by the detection of active oxygen and surface species in water. Phys. Chem. Chem. Phys. 2015, 17, 18691–18698. [Google Scholar] [CrossRef]
- Haque, F.Z.; Nandanwar, R.; Singh, P. Evaluating photodegradation properties of anatase and rutile TiO2 nanoparticles for organic compounds. Optik 2017, 128, 191–200. [Google Scholar] [CrossRef]
- Wang, Y.; Ganeshraja, A.S.; Jin, C.; Zhu, K.; Wang, J. One-pot synthesis visible-light-active TiO2 photocatalysts at low temperature by peroxotitanium complex. J. Alloys Compd. 2018, 765, 551–559. [Google Scholar] [CrossRef]
- Luo, S.; Wang, F.; Shi, Z.; Xin, F. Preparation of highly active photocatalyst anatase TiO2 by mixed template method. J. Sol-Gel Sci. Technol. 2009, 52, 1–7. [Google Scholar] [CrossRef]
- Praus, P.; Svoboda, L.; Ritz, M.; Troppová, I.; Šihor, M.; Kočí, K. Graphitic carbon nitride: Synthesis, characterization and photocatalytic decomposition of nitrous oxide. Mater. Chem. Phys. 2017, 193, 438–446. [Google Scholar] [CrossRef]
- Papailias, I.; Giannakopoulou, T.; Todorova, N.; Demotikali, D.; Vaimakis, T.; Trapalis, C. Effect of processing temperature on structure and photocatalytic properties of g-C3N4. Appl. Surf. Sci. 2015, 358, 278–286. [Google Scholar] [CrossRef]
- Precheza. PRETIOX Titanium Dioxide CG300 for catalytic preparation. Available online: https://www.precheza.cz/root/ke-stazeni/katalogy/letak-pretiox-titcg300-screen.pdf (accessed on 6 June 2019).
- Ohtani, B.; Prieto-Mahaney, O.O.; Li, D.; Abe, R. What is Degussa (Evonik) P25? Crystalline composition analysis, reconstruction from isolated pure particles and photocatalytic activity test. J. Photochem. Photobiol. A 2010, 216, 179–182. [Google Scholar] [CrossRef] [Green Version]
- Selloni, A.; Vittadini, A.; Grätzel, M. The adsorption of small molecules on the TiO2 anatase (101) surface by first-principles molecular dynamics. Surf. Sci. 1998, 402–404, 219–222. [Google Scholar] [CrossRef]
- Bolis, V.; Busco, C.; Ciarletta, M.; Distasi, C.; Erriquez, J.; Fenoglio, I.; Livraghi, S.; Morel, S. Hydrophilic/hydrophobic features of TiO2 nanoparticles as a function of crystal phase, surface area and coating, in relation to their potential toxicity in peripheral nervous system. J. Colloid Interface Sci. 2012, 369, 28–39. [Google Scholar] [CrossRef]
- Ohno, T.; Tokieda, K.; Higashida, S.; Matsumura, M. Synergism between rutile and anatase TiO2 particles in photocatalytic oxidation of naphthalene. Appl. Catal. A 2003, 244, 383–391. [Google Scholar] [CrossRef]
- Zhang, Y.; Gan, H.; Zhang, G. A novel mixed-phase TiO2/kaolinite composites and their photocatalytic activity for degradation of organic contaminants. Chem. Eng. J. 2011, 172, 936–943. [Google Scholar] [CrossRef]
- Rochkind, M.; Pasternak, S.; Paz, Y. Using dyes for evaluating photocatalytic properties: A critical review. Molecules 2014, 20, 88–110. [Google Scholar] [CrossRef]
- Konstantinou, I.K.; Albanis, T.A. TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: Kinetic and mechanistic investigations: A review. Appl. Catal. B 2004, 49, 1–14. [Google Scholar] [CrossRef]
- Kuznetsov, V.N.; Serpone, N. Visible Light Absorption by Various Titanium Dioxide Specimens. J. Phys. Chem. B 2006, 110, 25203–25209. [Google Scholar] [CrossRef]
- Kuznetsov, V.N.; Serpone, N. On the Origin of the Spectral Bands in the Visible Absorption Spectra of Visible-Light-Active TiO2 Specimens Analysis and Assignments. J. Phys. Chem. C 2009, 113, 15110–15123. [Google Scholar] [CrossRef]
- Janotti, A.; Varley, J.B.; Rinke, P.; Umezawa, N.; Kresse, G.; Van de Walle, C.G. Hybrid functional studies of the oxygen vacancy in TiO2. Phys. Rev. B 2010, 81, 085212. [Google Scholar] [CrossRef]
- Nakamura, I.; Negishi, N.; Kutsuna, S.; Ihara, T.; Sugihara, S.; Takeuchi, K. Role of oxygen vacancy in the plasma-treated TiO2 photocatalyst with visible light activity for NO removal. J. Mol. Catal. A Chem. 2000, 161, 205–212. [Google Scholar] [CrossRef]
- Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Fedorenko, L.; Kshnyakin, V.; Baran, J. Room temperature photoluminescence of anatase and rutile TiO2 powders. J. Lumin. 2014, 146, 199–204. [Google Scholar] [CrossRef]
- Scheytt, T.; Mersmann, P.; Lindstädt, R.; Heberer, T. 1-Octanol/Water Partition Coefficients of 5 Pharmaceuticals from Human Medical Care: Carbamazepine, Clofibric Acid, Diclofenac, Ibuprofen, and Propyphenazone. Water Air Soil Pollut. 2005, 165, 3–11. [Google Scholar] [CrossRef]
- Praus, P.; Veteška, M.; Pospíšil, M. Adsorption of phenol and aniline on natural and organically modified montmorillonite: Experiment and molecular modelling. Mol. Simul. 2011, 37, 964–974. [Google Scholar] [CrossRef]
- Bhatkhande, D.S.; Pangarkar, V.G.; Beenackers, A.A.C.M. Photocatalytic degradation for environmental applications – a review. J. Chem. Technol. Biotechnol. 2002, 77, 102–116. [Google Scholar] [CrossRef]
- Mills, A.; Le Hunte, S. An overview of semiconductor photocatalysis. J. Photochem. Photobiol. A 1997, 108, 1–35. [Google Scholar] [CrossRef]
- Brosillon, S.; Lhomme, L.; Vallet, C.; Bouzaza, A.; Wolbert, D. Gas phase photocatalysis and liquid phase photocatalysis: Interdependence and influence of substrate concentration and photon flow on degradation reaction kinetics. Appl. Catal. B 2008, 78, 232–241. [Google Scholar] [CrossRef]
- Wood, P.M. The potential diagram for oxygen at pH 7. Biochem. J 1988, 253, 287–289. [Google Scholar] [CrossRef]
- Kumar, K.V.; Porkodi, K.; Rocha, F. Langmuir–Hinshelwood kinetics – A theoretical study. Catal. Commun. 2008, 9, 82–84. [Google Scholar] [CrossRef]
- Moore, D.E.; Roberts-Thomson, S.; Zhen, D.; Duke, C.C. PHOTOCHEMICAL STUDIES ON THE ANTIINFLAMMATORY DRUG DICLOFENAC. Photochem. Photobiol. 1990, 52, 685–690. [Google Scholar] [CrossRef]
- Poiger, T.; Buser, H.-R.; Müller, M.D. Photodegradation of the pharmaceutical drug diclofenac in a lake: Pathway, field measurements, and mathematical modeling. Environ. Toxicol. Chem. 2001, 20, 256–263. [Google Scholar] [CrossRef]
- Vogna, D.; Marotta, R.; Napolitano, A.; Andreozzi, R.; d’Ischia, M. Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone. Water Res. 2004, 38, 414–422. [Google Scholar] [CrossRef]
Statistic | TiO2 CG300 | TiO2 P25 |
---|---|---|
Minimum (nm) | 2.3 | 10.6 |
Maximum (nm) | 6.0 | 32.6 |
Average (nm) | 4.0 | 20.5 |
Standard deviation (nm) | 0.83 | 5.1 |
Average confidence interval (nm) | 3.8–4.2 | 19.5–21.6 |
Skewness | 0.121 | 0.341 |
Kurtosis | 2.53 | 2.65 |
Pharmaceutical | Photodegradation (%) | |
---|---|---|
Paracetamol | ||
VIS | UV | |
P25 | 35 | 93 |
CG300 | 54 | 69 |
g-C3N4 | 54 | 41 |
Ibuprofen | ||
P25 | 17 | 99 |
CG300 | 13 | 94 |
g-C3N4 | 71 | 24 |
Diclofenac | ||
P25 | 25 | 96 |
CG300 | 49 | 66 |
g-C3N4 | 77 | 73 |
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Smýkalová, A.; Sokolová, B.; Foniok, K.; Matějka, V.; Praus, P. Photocatalytic Degradation of Selected Pharmaceuticals Using g-C3N4 and TiO2 Nanomaterials. Nanomaterials 2019, 9, 1194. https://doi.org/10.3390/nano9091194
Smýkalová A, Sokolová B, Foniok K, Matějka V, Praus P. Photocatalytic Degradation of Selected Pharmaceuticals Using g-C3N4 and TiO2 Nanomaterials. Nanomaterials. 2019; 9(9):1194. https://doi.org/10.3390/nano9091194
Chicago/Turabian StyleSmýkalová, Aneta, Barbora Sokolová, Kryštof Foniok, Vlastimil Matějka, and Petr Praus. 2019. "Photocatalytic Degradation of Selected Pharmaceuticals Using g-C3N4 and TiO2 Nanomaterials" Nanomaterials 9, no. 9: 1194. https://doi.org/10.3390/nano9091194