One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) with Improved Photocatalytic Activity for the Removal of Diclofenac from Water
Abstract
:1. Introduction
2. Materials and Methods
2.1. Preparation of Graphene Oxide (GO)
2.2. Solvothermal Synthesis of TiO2 and S-TiO2 Reduced Graphene Oxide Composite (S-TiO2/rGO)
2.3. Immobilization of S-TiO2/rGO Composites
2.4. Characterization of the S-TiO2/rGO Composite
2.5. Investigation of Photocatalytic Activity
3. Results and Discussion
3.1. Composition and Morphology of the S-TiO2/rGO Composite
3.2. Photocatalytic Performance of S-TiO2/rGO
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Jafari, T.; Moharreri, E.; Amin, A.S.; Miao, R.; Song, W.; Suib, S.L. Photocatalytic water splitting—the untamed dream: A review of recent advances. Molecules 2016, 21, 900. [Google Scholar] [CrossRef] [PubMed]
- Loeb, S.K.; Alvarez, P.J.J.; Brame, J.A.; Cates, E.L.; Choi, W.; Crittenden, J.; Dionysiou, D.D.; Li, Q.; Li-Puma, G.; Quan, X.; et al. The technology horizon for photocatalytic water treatment: Sunrise or sunset? Environ. Sci. Technol. 2019, 53, 2937–2947. [Google Scholar] [CrossRef] [PubMed]
- Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W. Understanding TiO2 photocatalysis: Mechanism and materials. Chem. Rev. 2014, 114, 9919–9986. [Google Scholar] [CrossRef] [PubMed]
- Bumajdad, A.; Madkour, M. Understanding the superior photocatalytic activity of noble metals modified titania under UV and visible light irradiation. Phys. Chem. Chem. Phys. 2014, 16, 7146. [Google Scholar] [CrossRef]
- Basavarajappa, P.S.; Patil, S.B.; Ganganagappa, N.; Reddy, K.R.; Raghu, A.V.; Reddy, C.V. Recent progress in metal-doped TiO2, non-metal doped/codoped TiO2 and nanostructured hybrids for enhanced photocatalysis. Int. J. Hydrog. Energy 2020, 45, 7764–7778. [Google Scholar] [CrossRef]
- Ge, J.; Zhang, Y.; Heo, Y.-J.; Park, S.-J. Advanced design and synthesis of composite photocatalysts for the remediation of wastewater: A review. Catalysts 2019, 9, 122. [Google Scholar] [CrossRef] [Green Version]
- Humayun, M.; Raziq, F.; Luo, W. Modification strategies of TiO2 for potential applications in photocatalysis: A critical review. Green Chem. Lett. Rev. 2018, 11, 86–201. [Google Scholar] [CrossRef] [Green Version]
- Žerjav, G.; Arshad, M.S.; Djinović, P.; Junkar, I.; Kovač, J.; Zavašnik, J.; Pintar, A. Improved electron-hole separation and migration in anatase TiO2 nanorod/reduced graphene oxide composites and their influence on photocatalytic performance. Nanoscale 2017, 9, 4578. [Google Scholar] [CrossRef] [Green Version]
- Minella, M.; Sordello, F.; Minero, C. Photocatalytic process in TiO2/graphene hybrid materials. Evidence of charge separation by electron transfer from reduced graphene oxide to TiO2. Catal. Today 2017, 281, 29–37. [Google Scholar] [CrossRef]
- Park, S.; An, J.; Potts, J.R.; Velamakanni, A.; Murali, S.; Ruoff, R.S. Hydrazine-reduction of graphite- and graphene oxide. Carbon 2011, 49, 3019–3023. [Google Scholar] [CrossRef]
- Sykam, N.; Madhavi, V.; Rao, G.M. Rapid and efficient green reduction of graphene oxide for outstanding supercapacitors and dye adsorption applications. J. Environ. Chem. Eng. 2018, 6, 3223–3232. [Google Scholar] [CrossRef]
- Giovanetti, R.; Rommozzi, E.; Zannotti, M.; D’Amato, C.A. Recent advances in graphene based TiO2 nanocomposites (GTiO2Ns) for Photocatalytic Degradation of Synthetic Dyes. Catalysts 2017, 7, 305. [Google Scholar] [CrossRef]
- Kong, D.; Zhao, M.; Li, S.; Huang, F.; Song, J.; Yuan, Y.; Shen, Y.; Xie, A. Synthesis of TiO2/rGO Nanocomposites with Enhanced Photoelectrochemical Performance and Photocatalytic Activity. Nano 2015, 11, 1650007. [Google Scholar] [CrossRef]
- Nainani, R.K.; Thakur, P. Facile synthesis of TiO2-RGO composite with enhanced performance for the photocatalytic mineralization of organic pollutants. Water. Sci. Technol. 2016, 73, 1927–1936. [Google Scholar] [CrossRef] [PubMed]
- Aqeel, M.S.; Imran, M.; Ikram, M.; Majeed, H.; Naz, M.; Ali, S.; Ahmad, M.A. TiO2@RGO (reduced graphene oxide) doped nanoparticles demonstrated improved photocatalytic activity. Mater. Res. Express 2019, 6, 086215. [Google Scholar] [CrossRef]
- Tajammul Hussain, S.; Khan, K.; Hussain, R. Size control synthesis of sulfur doped titanium dioxide (anatase) nanoparticles, its optical property and its photo catalytic reactivity for CO2 + H2O conversion and phenol degradation. J. Nat. Gas Chem. 2009, 18, 383–391. [Google Scholar] [CrossRef]
- Yu, J.; Liu, S.; Xiu, Z.; Yu, W.; Feng, G. Synthesis of sulfur-doped TiO2 by solvothermal method and its visible-light photocatalytic activity. J. Colloid Interface Sci. 2009, 471, L23–L25. [Google Scholar] [CrossRef]
- Liu, G.; Sun, C.; Smith, S.C.; Wang, L.; Qing, G.L.; Cheng, H.-M. Sulfur doped anatase TiO2 single crystals with a high percentage of {0 0 1} facets. J. Colloid Interface Sci. 2010, 349, 477–483. [Google Scholar] [CrossRef]
- Nam, S.-H.; Kim, T.K.; Boo, J.-H. Physical property and photo-catalytic activity of sulfur doped TiO2 catalysts responding to visible light. Catal. Today 2012, 185, 259–262. [Google Scholar] [CrossRef]
- Gomathi Devi, L.; Kavitha, R. Enhanced photocatalytic activity of sulfur doped TiO2 for the decomposition of phenol: A new insight into the bulk and surface modification. Mater. Chem. Phys. 2014, 143, 1300–1308. [Google Scholar] [CrossRef]
- Hummers, W.S.; Offeman, R.E. Preparation of graphitic oxide. J. Am. Chem. Soc. 1958, 80, 1339. [Google Scholar] [CrossRef]
- Kete, M.; Pavlica, E.; Fresno, F.G.; Bratina, U. Lavrencic Stangar, Highly active photocatalytic coatings prepared by a low-temperature method. Environ. Sci. Pollut. Res. 2014, 21, 11238–11249. [Google Scholar] [CrossRef] [PubMed]
- Patterson, A.L. The Scherrer formula for X-ray particle size determination. Phys. Rev. 1939, 56, 978–982. [Google Scholar] [CrossRef]
- Moghaddam, H.M.; Nasirian, S. Dependence of activation energy and lattice strain on TiO2 nanoparticles? Nanosci. Methods 2012, 1, 201–212. [Google Scholar] [CrossRef]
- López, R.; Gómez, R. Band-gap energy estimation from diffuse reflectance measurements on sol-gel and commercial TiO2: A comparative study. J. Sol-Gel Sci. Technol. 2012, 61, 1–7. [Google Scholar] [CrossRef]
- Radón, A.; Włodarczyk, P.; Łukowiec, D. Structure, temperature and frequency dependent electrical conductivity of oxidized and reduced electrochemically exfoliated graphite. Phys. E 2018, 99, 82–90. [Google Scholar] [CrossRef]
- Kudin, K.N.; Ozbas, B.; Schniepp, H.C.; Prud’homme, R.K.; Aksay, I.A.; Car, R. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett. 2008, 8, 36–41. [Google Scholar] [CrossRef]
- Suave, J.; Amorim, S.M.; Ângelo, J.; Andrade, L.; Mendes, A.; Moreira, R.F.P.M. TiO2/reduced graphene oxide composites for photocatalytic degradation in aqueous and gaseous medium. J. Photochem. Photobiol. A 2017, 348, 326–336. [Google Scholar] [CrossRef]
- Cravanzola, S.; Cesano, F.; Gaziano, F.; Scarano, D. Sulfur-doped TiO2: Structure and surface properties. Catalysts 2017, 7, 214. [Google Scholar] [CrossRef] [Green Version]
- Lin, H.; Huang, C.P.; Li, W.; Ni, C.; Ismat Shah, S.; Tseng, Y.-H. Size dependency of nanocrystalline TiO2 on its optical property and photocatalytic reactivity exemplified by 2-chlorophenol. Appl. Catal. B 2006, 68, 1–11. [Google Scholar] [CrossRef]
- Liu, Y. Hydrothermal synthesis of TiO2-RGO composites and their improved photocatalytic activity in visible light. RSC Adv. 2014, 4, 36040. [Google Scholar] [CrossRef]
- Pallotti, D.K.; Passoni, L.; Maddalena, P.; Di Fonzo, F.; Lettieri, S. Photoluminescence mechanisms in anatase and rutile TiO2. J. Phys. Chem. C 2017, 121, 9011–9021. [Google Scholar] [CrossRef]
- Liu, Q.-L.; Zhao, Z.-Y.; Liu, Q.-J. Analysis of sulfur modification mechanism for anatase and rutile TiO2 by different doping modes based on GGA + U calculation. RSC Adv. 2014, 4, 32100–32107. [Google Scholar] [CrossRef]
- Kovacic, M.; Kusic, H.; Fanetti, M.; Lavrencic Stangar, U.; Valant, M.; Dionysiou, D.D.; Loncaric Bozic, A. TiO2-SnS2 nanocomposites: Solar-active photocatalytic materials for water treatment. Environ. Sci. Pollut. Res. 2017, 24, 19965–19979. [Google Scholar] [CrossRef] [PubMed]
- Rajagopal, R.; Ryu, K.-S. Synthesis of rGO-doped Nb4O5-TiO2 nanorods for photocatalytic and electrochemical storage applications. Appl. Catal. B 2018, 236, 125–139. [Google Scholar] [CrossRef]
- Kusiak-Nejman, E.; Wanag, A.; Kapica-Kozar, J.; Kowalczyk, Ł.; Zgrzebnicki, M.; Tryba, B.; Przepiórski, J.; Morawski, A.W. Methylene blue decomposition on TiO2/reduced graphene oxide hybrid photocatalysts obtained by a two-step hydrothermal and calcination synthesis. Catal. Today 2019, in press. [Google Scholar] [CrossRef]
- Wang, W.; Wang, Z.; Liu, J.; Luo, Z.; Suib, S.L.; He, P.; Ding, G.; Zhang, Z.; Sun, L. Single step one-pot synthesis of TiOS nanosheets doped with sulfur on reduced graphene oxide with enhanced photocatalytic activity. Sci. Rep. 2017, 7, 46610. [Google Scholar] [CrossRef] [Green Version]
- Kovacic, M.; Katic, J.; Kusic, H.; Loncaric Bozic, A.; Metikos Hukovic, M. Elucidating the photocatalytic behavior of TiO2-SnS2 composites based on their energy band structure (Supplementary). Materials 2018, 11, 1041. [Google Scholar] [CrossRef] [Green Version]
- Zhang, Y.C.; Li, J.; Xu, H.Y. One-step in situ solvothermal synthesis of SnS2/TiO2 nanocomposites with high performance in visible light-driven photocatalytic reduction of aqueous Cr(VI). Appl. Catal. B 2012, 123–124, 18–26. [Google Scholar] [CrossRef]
- Alazmi, A.; El Tall, O.; Rasul, S.; Hedhili, M.N.; Patole, S.P.; Costa, P.M.F.J. A process to enhance the specific surface area and capacitance of hydrothermally reduced graphene oxide. Nanoscale 2016, 8, 17782–17787. [Google Scholar] [CrossRef]
- Tayel, A.; Ramadan, A.R.; El Seoud, O.A. Titanium dioxide/graphene and titanium dioxide/graphene oxide nanocomposites: Synthesis, characterization and photocatalytic applications for water decontamination. Catalysts 2018, 8, 491. [Google Scholar] [CrossRef] [Green Version]
- Orth, E.S.; Ferreira, J.G.L.; Fonsaca, J.E.S.; Blaskievicz, S.F.; Domingues, S.H.; Dasgupta, A.; Terrones, M.; Zarbin, A.J.G. pKa determination of graphene-like materials: Validating chemical functionalization. J. Colloid Interface Sci. 2016, 467, 239–244. [Google Scholar] [CrossRef] [PubMed]
Sample | a, Å | c, Å | d101, Å | d004, Å | d200, Å | Cell Volume, Å3 | τ, nm |
---|---|---|---|---|---|---|---|
TiO2 | 3.798 | 9.515 | 3.531 | 2.379 | 1.899 | 137.26 | 17.5 |
S-TiO2/rGO(5.0%) | 3.787 | 9.454 | 3.516 | 2.363 | 1.894 | 135.56 | 13.4 |
w(rGO), % | BET Surface Area, m2 g−1 |
---|---|
0.0 | 128.4 ± 1.9 [38] |
0.5 | 123.2 ± 1.6 |
2.75 | 128.9 ± 1.4 |
5.0 | 131.9 ± 1.8 |
100.0 | 17.1 ± 0.19 |
© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Kovačić, M.; Perović, K.; Papac, J.; Tomić, A.; Matoh, L.; Žener, B.; Brodar, T.; Capan, I.; Surca, A.K.; Kušić, H.; et al. One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) with Improved Photocatalytic Activity for the Removal of Diclofenac from Water. Materials 2020, 13, 1621. https://0-doi-org.brum.beds.ac.uk/10.3390/ma13071621
Kovačić M, Perović K, Papac J, Tomić A, Matoh L, Žener B, Brodar T, Capan I, Surca AK, Kušić H, et al. One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) with Improved Photocatalytic Activity for the Removal of Diclofenac from Water. Materials. 2020; 13(7):1621. https://0-doi-org.brum.beds.ac.uk/10.3390/ma13071621
Chicago/Turabian StyleKovačić, Marin, Klara Perović, Josipa Papac, Antonija Tomić, Lev Matoh, Boštjan Žener, Tomislav Brodar, Ivana Capan, Angelja K. Surca, Hrvoje Kušić, and et al. 2020. "One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) with Improved Photocatalytic Activity for the Removal of Diclofenac from Water" Materials 13, no. 7: 1621. https://0-doi-org.brum.beds.ac.uk/10.3390/ma13071621