Synthesis and Application of Chitosan–Graphene Oxide and Titanium-Dioxide Coated Granular Activated Carbon Composites for Adsorptive and Photocatalytic Removal of Antibiotics
Publication: Journal of Hazardous, Toxic, and Radioactive Waste
Volume 25, Issue 4
Abstract
The main aim of this study was to remove a model antibiotic, that is, metronidazole (MET), using TiO2 coated on granular activated charcoal (GAC–TiO2) and graphene oxide (GO) embedded in chitosan (CS) by adsorption and photocatalysis. Analyses including scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, Fourier transform Ramen spectroscopy, X-ray diffraction, and the BET method, along with batch adsorption and photocatalysis results, were used to compare the performance of composites. The ultraviolet C (UVC)/CS–GO system (99.4%) showed higher MET removal compared with UVC/GAC–TiO2 (97.4%) at 10 mg L−1 initial MET concentration; however, the total organic carbon reduction was greater in the GAC–TiO2 system (78.4%) than in the CS–GO system (72.3%). After 120 min, the UVC/GAC–TiO2 and UVC/CS–GO systems showed maximum MET removal rates of 0.0561 and 0.04 min−1, respectively. By contrast, batch adsorption experiments indicated that CS–GO has approximately 20 times greater MET adsorption capacity than GAC–TiO2. Furthermore, CS–GO was found to be superior in MET removal than GAC–TiO2 in a reusability study (i.e., for 15 treatment cycles), owing to higher adsorption capacity. Overall, the results indicate that CS–GO could be a potential composite for continuous photocatalytic experiments in the framework of emerging contaminant removal.
Get full access to this article
View all available purchase options and get full access to this article.
Acknowledgments
This study was funded by the ICSR, IIT Madras (Grant No. CIE/14-15/832/NFIG/SMAT) and WTI, DST, India (Grant No. DST/TM/WTI/2K15/192).
References
Abedi, K. a. D., F. Ghorbani-Shahna, A. Bahrami, H. Ebrahimi, A. Maleki, F. Madjidi, S. Musavi, E. Mohammadi, and O. Giahi. 2018. “Effect of TiO2/GAC and water vapor on chloroform decomposition in a hybrid plasma-catalytic system.” Environ. Technol. 39 (16): 2041–2050. https://doi.org/10.1080/09593330.2017.1349185.
Andriantsiferana, C., E. F. Mohamed, and H. Delmas. 2014. “Photocatalytic degradation of an azo-dye on TiO2/activated carbon composite material.” Environ. Technol. 35 (3): 355–363. https://doi.org/10.1080/09593330.2013.828094.
Arlos, M. J., M. M. Hatat-Fraile, R. Liang, L. M. Bragg, N. Y. Zhou, S. A. Andrews, and M. R. Servos. 2016. “Photocatalytic decomposition of organic micropollutants using immobilized TiO2 having different isoelectric points.” Water Res. 101: 351–361. https://doi.org/10.1016/j.watres.2016.05.073.
Asha, R. C., and M. Kumar. 2015. “Sulfamethoxazole in poultry wastewater: Identification, treatability and degradation pathway determination in a membrane-photocatalytic slurry reactor.” J. Environ. Sci. Health, Part A 50 (10): 1011–1019. https://doi.org/10.1080/10934529.2015.1038161.
Ashkarran, A. A., M. Fakhari, H. Hamidinezhad, H. Haddadi, and M. R. Nourani. 2015. “TiO2 nanoparticles immobilized on carbon nanotubes for enhanced visible-light photo-induced activity.” J. Mater. Res. Technol. 4 (2): 126–132. https://doi.org/10.1016/j.jmrt.2014.10.005.
Authority, P. B. Y. 2020. “The Gazette of LITEdia. 1935(D).” Accessed March 12, 2021. http://moef.gov.in/wp-content/uploads/2020/01/finalization.pdf.
Barkin, J. A., D. A. Sussman, N. Fifadara, and J. S. Barkin. 2017. “Clostridium difficile infection and patient-specific antimicrobial resistance testing reveals a high metronidazole resistance rate.” Digestive Dis. Sci. 62 (4): 1035–1042. https://doi.org/10.1007/s10620-017-4462-9.
Basha, S., D. Keane, A. Morrissey, K. Nolan, M. Oelgemöller, and J. Tobin. 2010. “Studies on the adsorption and kinetics of photodegradation of pharmaceutical compound, indomethacin using novel photocatalytic adsorbents (IPCAs).” Ind. Eng. Chem. Res. 49 (22): 11302–11309. https://doi.org/10.1021/ie101304a.
Borges, M. E., M. Sierra, E. Cuevas, R. D. García, and P. Esparza. 2016. “Photocatalysis with solar energy: Sunlight-responsive photocatalyst based on TiO2 loaded on a natural material for wastewater treatment.” Sol. Energy 135: 527–535. https://doi.org/10.1016/j.solener.2016.06.022.
Brandt, K. K., et al. 2015. “Ecotoxicological assessment of antibiotics: A call for improved consideration of microorganisms.” Environ. Int. 85: 189–205. https://doi.org/10.1016/j.envint.2015.09.013.
Cao, N., and Y. Zhang. 2015. “Study of reduced graphene oxide preparation by hummers’ method and related characterization.” J. Nanomater. 2015: 168125. https://doi.org/10.1155/2015/168125.
Dakshinamoorthy, P., and S. Vaithilingam. 2017. “Platinum-copper doped poly(sulfonyldiphenol/cyclophosphazene/benzidine)-graphene oxide composite as an electrode material for single stack direct alcohol alkaline fuel cells.” RSC Adv. 7 (56): 34922–34932. https://doi.org/10.1039/C7RA04525E.
Farzadkia, M., E. Bazrafshan, A. Esrafili, J. K. Yang, and M. Shirzad-Siboni. 2015. “Photocatalytic degradation of Metronidazole with illuminated TiO2 nanoparticles.” J. Environ. Heal. Sci. Eng. 13 (1): 1–8. https://doi.org/10.1186/s40201-015-0194-y.
Girgis, B. S., Y. M. Temerk, M. M. Gadelrab, and I. D. Abdullah. 2007. “X-ray diffraction patterns of activated carbons prepared under various conditions.” Carbon Lett. 8 (2): 95–100. https://doi.org/10.5714/CL.2007.8.2.095.
Haque, F., E. Vaisman, C. H. Langford, and A. Kantzas. 2005. “Preparation and performance of integrated photocatalyst adsorbent (IPCA) employed to degrade model organic compounds in synthetic wastewater.” J. Photochem. Photobiol., A 169 (1): 21–27. https://doi.org/10.1016/j.jphotochem.2004.05.019.
Jiang, Y., J. L. Gong, G. M. Zeng, X. M. Ou, Y. N. Chang, C. H. Deng, J. Zhang, H. Y. Liu, and S. Y. Huang. 2016. “Magnetic chitosan-graphene oxide composite for anti-microbial and dye removal applications.” Int. J. Biol. Macromol. 82: 702–710. https://doi.org/10.1016/j.ijbiomac.2015.11.021.
Kakavandi, B., N. Bahari, R. Rezaei Kalantary, and E. Dehghani Fard. 2019. “Enhanced sono-photocatalysis of tetracycline antibiotic using TiO2 decorated on magnetic activated carbon (MAC@T) coupled with US and UV: A new hybrid system.” Ultrason. Sonochem. 55: 75–85. https://doi.org/10.1016/j.ultsonch.2019.02.026.
Kamal, M. A., S. Bibi, S. W. Bokhari, A. H. Siddique, and T. Yasin. 2017. “Synthesis and adsorptive characteristics of novel chitosan/graphene oxide nanocomposite for dye uptake.” React. Funct. Polym. 110: 21–29. https://doi.org/10.1016/j.reactfunctpolym.2016.11.002.
Kanakaraju, D., J. Kockler, C. A. Motti, B. D. Glass, and M. Oelgemöller. 2015. “Titanium dioxide/zeolite integrated photocatalytic adsorbents for the degradation of amoxicillin.” Appl. Catal., B 166–167: 45–55. https://doi.org/10.1016/j.apcatb.2014.11.001.
Keane, D., S. Basha, K. Nolan, A. Morrissey, M. Oelgemöller, and J. M. Tobin. 2011. “Photodegradation of famotidine by integrated photocatalytic adsorbent (IPCA) and kinetic study.” Catal. Lett. 141 (2): 300–308. https://doi.org/10.1007/s10562-010-0485-y.
Kumar, A. S. K., and S. J. Jiang. 2016. “Chitosan-functionalized graphene oxide: A novel adsorbent an efficient adsorption of arsenic from aqueous solution.” J. Environ. Chem. Eng. 4 (2): 1698–1713. https://doi.org/10.1016/j.jece.2016.02.035.
Li, Y., X. Li, J. Li, and J. Yin. 2006. “Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study.” Water Res. 40 (6): 1119–1126. https://doi.org/10.1016/j.watres.2005.12.042.
Lv, C., J. Shi, Q. Tang, and Q. Hu. 2020. “Tetracycline removal by activating persulfate with diatomite loading of Fe and Ce.” Molecules 25 (23): 5531. https://doi.org/10.3390/molecules25235531.
Neghi, N., N. R. Krishnan, and M. Kumar. 2018. “Analysis of metronidazole removal and micro-toxicity in photolytic systems: Effects of persulfate dosage, anions and reactor operation-mode.” J. Environ. Chem. Eng. 6 (1): 754–761. https://doi.org/10.1016/j.jece.2017.12.072.
Neghi, N., and M. Kumar. 2017. “Performance analysis of photolytic, photocatalytic, and adsorption systems in the degradation of metronidazole on the perspective of removal rate and energy consumption.” Water Air Soil Pollut. 228 (9): 339. https://doi.org/10.1007/s11270-017-3532-0.
Peng, B., L. Chen, C. Que, K. Yang, F. Deng, X. Deng, G. Shi, G. Xu, and M. Wu. 2016. “Adsorption of antibiotics on graphene and biochar in aqueous solutions induced by π-π interactions.” Sci. Rep. 6 (1): 31920. https://doi.org/10.1038/srep31920.
Putri, L. K., L. L. Tan, W. J. Ong, W. S. Chang, and S. P. Chai. 2016. “Graphene oxide: Exploiting its unique properties toward visible-light-driven photocatalysis.” Appl. Mater. Today 4: 9–16. https://doi.org/10.1016/j.apmt.2016.04.001.
Salameh, C., J. P. Nogier, F. Launay, and M. Boutros. 2015. “Dispersion of colloidal TiO2 nanoparticles on mesoporous materials targeting photocatalysis applications.” Catal. Today 257: 35–40. https://doi.org/10.1016/j.cattod.2015.03.025.
Schneider, J., M. Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo, and D. W. Bahnemann. 2014. “Understanding TiO2 photocatalysis mechanisms and materials.” Chem. Rev. 114 (9): 9919–9986. https://doi.org/10.1021/cr5001892.
Shahnaz, T., V. Sharma, S. Subbiah, and S. Narayanasamy. 2020. “Multivariate optimisation of Cr (VI), Co (III) and Cu (II) adsorption onto nanobentonite incorporated nanocellulose/chitosan aerogel using response surface methodology.” J. Water Process Eng. 36: 101283. https://doi.org/10.1016/j.jwpe.2020.101283.
Sheng, Y., X. Tang, E. Peng, and J. Xue. 2013. “Graphene oxide based fluorescent nanocomposites for cellular imaging.” J. Mater. Chem. B 1 (4): 512–521. https://doi.org/10.1039/C2TB00123C.
Sin, J. C., S. M. Lam, and A. R. Mohamed. 2011. “Optimizing photocatalytic degradation of phenol by TiO2/GAC using response surface methodology.” Korean J. Chem. Eng. 28 (1): 84–92. https://doi.org/10.1007/s11814-010-0318-0.
Sponza, D. T., and P. Alicanoglu. 2018. “Reuse and recovery of raw hospital wastewater containing ofloxacin after photocatalytic treatment with nano graphene oxide magnetite.” Water Sci. Technol. 77 (2): 304–322. https://doi.org/10.2166/wst.2017.531.
Tang, J., J. R. Durrant, and D. R. Klug. 2008. “Mechanism of photocatalytic water splitting in TiO2. Reaction of water with photoholes, importance of charge carrier dynamics, and evidence for four-hole chemistry.” J. Am. Chem. Soc. 130 (42): 13885–13891. https://doi.org/10.1021/ja8034637.
Tran, M. L., C. C. Fu, and R. S. Juang. 2019. “Effects of water matrix components on degradation efficiency and pathways of antibiotic metronidazole by UV/TiO2 photocatalysis.” J. Mol. Liq. 276: 32–38. https://doi.org/10.1016/j.molliq.2018.11.155.
Velasco, L. F., I. M. Fonseca, J. B. Parra, J. C. Lima, and C. O. Ania. 2012. “Photochemical behaviour of activated carbons under UV irradiation.” Carbon 50 (1): 249–258. https://doi.org/10.1016/j.carbon.2011.08.042.
Velasco, L. F., V. Maurino, E. Laurenti, I. M. Fonseca, J. C. Lima, and C. O. Ania. 2013. “Photoinduced reactions occurring on activated carbons. A combined photooxidation and ESR study.” Appl. Catal., A 452: 1–8. https://doi.org/10.1016/j.apcata.2012.11.033.
Velo-Gala, I., J. J. López-Peñalver, M. Sánchez-Polo, and J. Rivera-Utrilla. 2014. “Role of activated carbon on micropollutans degradation by ionizing radiation.” Carbon 67: 288–299. https://doi.org/10.1016/j.carbon.2013.09.091.
Vishnuganth, M. A., N. Remya, M. Kumar, and N. Selvaraju. 2016. “Photocatalytic degradation of carbofuran by TiO2-coated activated carbon: Model for kinetic, electrical energy per order and economic analysis.” J. Environ. Manage. 181: 201–207. https://doi.org/10.1016/j.jenvman.2016.06.016.
Wang, Y., L. L. Li, C. Luo, X. Wang, and H. Duan. 2016. “Removal of Pb2+ from water environment using a novel magnetic chitosan/graphene oxide imprinted Pb2+.” Int. J. Biol. Macromol. 86: 505–511. https://doi.org/10.1016/j.ijbiomac.2016.01.035.
Xing, B., C. Shi, C. Zhang, G. Yi, L. Chen, H. Guo, G. Huang, and J. Cao. 2016. “Preparation of TiO2/activated carbon composites for photocatalytic degradation of RhB under UV light irradiation.” J. Nanomater. 2016: 8393648. https://doi.org/10.1155/2016/8393648.
Zając, A., J. Hanuza, M. Wandas, and L. Dymińska. 2015. “Determination of N-acetylation degree in chitosan using Raman spectroscopy.” Spectrochim. Acta, Part A 134: 114–120. https://doi.org/10.1016/j.saa.2014.06.071.
Zhang, L., H. Luo, P. Liu, W. Fang, and J. Geng. 2016. “A novel modified graphene oxide/chitosan composite used as an adsorbent for Cr(VI) in aqueous solutions.” Int. J. Biol. Macromol. 87: 586–596. https://doi.org/10.1016/j.ijbiomac.2016.03.027.
Information & Authors
Information
Published In
Journal of Hazardous, Toxic, and Radioactive Waste
Volume 25 • Issue 4 • October 2021
Copyright
© 2021 American Society of Civil Engineers.
History
Received: Dec 15, 2020
Accepted: Apr 19, 2021
Published online: Jun 4, 2021
Published in print: Oct 1, 2021
Discussion open until: Nov 4, 2021
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.
Cited by
- Dinkar Parashar, Afrah Harafan, Gopal Achari, Mathava Kumar, Ciprofloxacin and Metronidazole Adsorption on Chitosan-Modified Graphene Oxide as Single-Compound and Binary Mixtures: Kinetics, Isotherm, and Sorption Mechanism, Journal of Hazardous, Toxic, and Radioactive Waste, 10.1061/(ASCE)HZ.2153-5515.0000724, 27, 1, (2023).
- Rajat Chatterjee, Chanchal Majumder, Application of modified graphene oxide-chitosan composite for the removal of 2-methylpyridine using fixed bed adsorption and subsequent regeneration of the adsorbent by UV photolysis, Journal of Water Process Engineering, 10.1016/j.jwpe.2023.103654, 53, (103654), (2023).
- Weiquan Liao, Meihua Zhao, Hongwei Rong, Peng Jiang, Quan Liao, Chaosheng Zhang, Yiting Chen, Photocatalyst immobilized by hydrogel, efficient degradation and self regeneration: A review, Materials Science in Semiconductor Processing, 10.1016/j.mssp.2022.106929, 150, (106929), (2022).