Fabrication and application of mgfe2o4 wo3 rgo nanocomposite as an advanced photocatalyst for antibiotic degradation in aqueous solutions

VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY NGHIEM XUAN DUC FABRICATION AND APPLICATION OF MgFe2O4/WO3/rGO NANOCOMPOSITE AS AN ADVANCED PHOTOCATALYST FOR ANTIBIOTIC DEGRADATION IN AQUEOUS SOLUTIONS MASTER'S THESIS VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY NGHIEM XUAN DUC FABRICATION AND APPLICATION OF MgFe2O4/WO3/rGO NANOCOMPOSITE AS AN ADVANCED PHOTOCATALYST FOR ANTIBIOTIC DEGRADATION IN AQUEOUS SOLUTIONS MAJOR: ENVIRONMENTAL ENGINEERING CODE: 8520320.01 RESEARCH SUPERVISORS: Associate Prof Dr TRAN DINH TRINH Dr NGUYEN THI AN HANG Hanoi, 2022 COMMITMENT I have read and understood the plagiarism violations I pledge with personal honor that this research result is my own and does not violate the Regulation on prevention of plagiarism in academic and scientific research activities at VNU Vietnam Japan University (Issued together with Decision No 700/QD-ĐHVN dated 30/9/2021 by the Rector of Vietnam Japan University) Author of the thesis ACKNOWLEDGEMENTS This research would not have been possible without the guidance, support, and patience of a number of individuals with whom I have had the honor of engaging and learning over the years Before anything else, I would like to express my profound appreciation to Associate Professor Tran Dinh Trinh and Doctor Nguyen Thi An Hang for their enthusiastic instruction and supervision throughout this research Secondly, I would like to take this opportunity to thank all of the professors, lecturers, and students in the Master’s Program in Environmental Engineering at VNU Vietnam Japan University for their assistance and encouragement during this work, which has been fully appreciated Lastly, I would like to thank my closest friends Thao, Huong, Dai and Hoang Anh for their support and encouragement throughout this lengthy journey TABLE OF CONTENTS List of tables i List of figures ii List of abbreviations iv Chapter Introduction 1.1 Research significance 1.2 Research novelty 1.3 Research objectives 1.4 Thesis structure Chapter Literature review 2.1 Ciprofloxacin pollution in aquatic environment 2.1.1 Introduction of Ciprofloxacin (CIP) 2.1.2 Occurrence of CIP in aquatic environment 2.1.3 Negative impacts of CIP on aquatic medium 11 2.2 Methods for treatment of CIP in aquatic medium 12 2.2.1 Conventional methods 12 2.2.2 Advanced Oxidation Processes (AOP) by photocatalyst 15 2.3 Introduction of MgFe2O4 nanoparticle 16 2.4 Introduction of WO3 nanoparticle 22 2.5 Introduction of reduced graphene oxide (rGO) 23 2.6 Overview of Z-scheme photocatalytic system 26 2.7 MgFe2O4/WO3/rGO nanoparticle as a direct Z-scheme photocatalytic system 28 2.8 Conclusion of literature review 29 Chapter Materials and methods 31 3.1 Chemicals and Apparatus 31 3.1.1 Chemicals 31 3.1.2 Apparatus 31 3.2 Material synthesis 32 3.2.1 Synthesis of MgFe2O4 32 3.2.2 Synthesis of WO3 32 3.2.3 Synthesis of GO 32 3.2.4 Synthesis of MgFe2O4/WO3/rGO nanocomposite 33 3.3 Material characterization method 33 3.3.1 X-ray Diffraction 33 3.3.2 Fourier-transform infrared spectroscopy 35 3.3.3 Scanning electron microscope 36 3.3.4 Energy-dispersive X-ray spectroscopy 37 3.3.5 UV–Vis Diffuse Reflectance Spectroscopy 38 3.3.6 Photoluminescence 40 3.3.7 pH point of zero charge 40 3.4 Study of photocatalytic removal of Ciprofloxacin by MgFe 2O4-WO3-rGO nanocomposite 41 3.4.1 Determination of Ciprofloxacin concentration 41 3.4.2 Determine efficiency of Ciprofloxacin removal 43 3.4.3 Comparative study of CIP removal by MgFe 2O4, WO3 and MgFe2O4/WO3/rGO 43 3.4.4 Factors influencing the CIP removal efficiency 43 3.4.5 Kinetic study 44 3.4.6 Radical scavengers 45 3.4.7 Stability and recyclability of MgFe 2O4/WO3/rGO nanocomposite 45 Chapter Results and discussion 46 4.1 Material characterization 46 4.1.1 X-ray Diffraction 46 4.1.2 Fourier-transform infrared spectroscopy 47 4.1.3 Scanning electron microscope 48 4.1.4 Energy-dispersive X-ray spectroscopy 50 4.1.5 UV–Vis Diffuse Reflectance Spectroscopy 53 4.1.6 Photoluminescence 55 4.1.7 pH point of zero charge 56 4.2 Study of photocatalytic removal of Ciprofloxacin by MgFe 2O4-WO3-rGO nanocomposite 57 4.2.1 Comparative study on the removal of CIP by MgFe 2O4, WO3 and MgFe2O4/WO3/rGO 57 4.2.2 Factors influencing the CIP removal efficiency 58 4.2.3 Kinetic study of CIP photodegradation 65 4.2.4 Radical scavengers and proposed mechanism of CIP photodegradation process 67 4.2.5 Stability and recyclability of MgFe 2O4/WO3/rGO nanocomposite 70 Chapter Conclusion and recommendations 72 Reference 74 LIST OF TABLES Table 2.1 Antibiotics and their respective highest concentration in Vietnam Table 2.2 Methods for removal of CIP from aqueous solutions 13 Table 2.3 The positions of cations, formula and example of normal, inverse and mixed spinel ferrites 17 Table 2.4 Chemical synthesis methods of spinel ferrites 20 Table 2.5 Different method for synthesis of GO 24 Table 2.6 Different methods for synthesis of rGO 25 Table 2.7 Comparison of three generations of Z-scheme photocatalytic system 26 Table 4.1 Elemental composition of MgFe2O4/WO3/rGO nanocomposite 52 Table 4.2 Eg of MgFe2O4, WO3 and MgFe2O4/WO3/rGO 55 Table 4.3 The comparison of CIP photodegradation between MgFe 2O4/WO3/rGO nanocomposite and other photocatalysts 64 i LIST OF FIGURES Figure 2.1 Structure of CIP Figure 2.2 Species of CIP at different pH values Figure 2.3 The amount of antibiotics imported into Vietnam Figure 2.4 Sources of CIP in aquatic medium Figure 2.5 Schematic diagram of AOP 16 Figure 2.6 Diagram of spinel ferrite demonstrating tetrahedral (yellow), octahedral (green) and oxygen atoms (red) units 18 Figure 2.7 Crystallite structure of WO3 at different temperature 22 Figure 2.8 Chemical structure of GO 24 Figure 2.9 Historical progression of Z-scheme photocatalytic system 26 Figure 2.10 Mechanism of a direct Z-scheme photocatalytic system 28 Figure 3.1 Operation of XRD method 34 Figure 3.2 XRD MiniFlex 600, Rigaku Corp 35 Figure 3.3 FT-IR 4600, Jasco Corp 36 Figure 3.4 Schematic diagram of a FT-IR instrument 36 Figure 3.5 SEM TM 4000 Plus, Hitachi Corp 37 Figure 3.6 Fundamental principle of EDX instrument 38 Figure 3.7 EDX MisF+, Oxford Instruments plc 38 Figure 3.8 UV-Vis DRS UH 5300, Hitachi Corp 39 Figure 3.9 FluoroMax-4, Horiba 40 Figure 3.10 Calibration curve of CIP 42 Figure 3.11 Schematic diagram of CIP degradation by photocatalyst 43 Figure 4.1 XRD spectra of MgFe2O4, WO3, rGO and MgFe2O4/WO3/rGO 47 Figure 4.2 FT-IR spectra of MgFe2O4, WO3, rGO and MgFe2O4/WO3/rGO 48 Figure 4.3 SEM image of MgFe2O4 49 Figure 4.4 SEM image of WO3 49 Figure 4.5 SEM image of MgFe2O4/WO3/rGO 50 Figure 4.6 EDX spectrum of MgFe2O4/WO3/rGO 51 Figure 4.7 Electron mapping of a) Mg, b) C, c) Fe, d) O, and e) W elements in the MgFe2O4/WO3/rGO nanocomposite 52 Figure 4.8 UV-Vis DRS absorption spectra of MgFe2O4, WO3 and MgFe2O4/WO3/rGO 53 Figure 4.9 Tauc plot of MgFe2O4, WO3 and MgFe2O4/WO3/rGO 54 Figure 4.10 Photoluminescene spectra of MgFe 2O4/WO3/rGO nanocomposite and pristine MgFe2O4 nanoparticle 56 Figure 4.11 pHpzc of MgFe2O4/WO3/rGO nanocomposite 57 Figure 4.12 Comparison of CIP removal between MgFe2O4, WO3, and MgFe2O4/WO3/rGO 58 ii Figure 4.13 Comparison of CIP removal by MgFe2O4/WO3/rGO nanocomposite at various pH values 59 Figure 4.14 CIP species at different pH value 60 Figure 4.15 Comparison of CIP removal at various dosage of MgFe 2O4/WO3/rGO nanocomposite 62 Figure 4.16 Comparison of CIP removal at various initial CIP concentration by MgFe2O4/WO3/rGO nanocomposite 63 Figure 4.17 Pseudo-zero-order kinetic model for CIP-photodegradation by MgFe2O4/WO3/rGO nanocomposite 66 Figure 4.18 Pseudo-first-order kinetic model for CIP-photodegradation by MgFe2O4/WO3/rGO nanocomposite 66 Figure 4.19 Pseudo-second-order kinetic model for CIP-photodegradation by MgFe2O4/WO3/rGO nanocomposite 67 Figure 4.20 Comparison between CIP removal with or without t-BuOH by MgFe2O4/WO3/rGO nanocomposite 68 Figure 4.21 Proposed mechanism for CIP photodegradation by MgFe2O4/WO3/rGO nanocomposite 69 Figure 4.22 MgFe2O4/WO3/rGO (a) before and (b) after extracted by magnet 70 Figure 4.23 Stability and recyclability of MgFe2O4/WO3/rGO nanocomposite after three cycles 70 iii LIST OF ABBREVIATIONS AOP: Advanced Oxidation Processes BSE: Backscattered electron CB: Conduction band CIP: Ciprofloxacin COD: Chemical Oxygen Demand EDX: Energy-dispersive X-ray Eg: Band gap energy FT-IR: Fourier-transform infrared spectroscopy GO: Graphene oxide KLAMG: VNU Key Laboratory for Advanced Materials for Green Growth MARD: Ministry of Agriculture and Rural Development NHE: Normal hydrogen electrode pHpzc: pH point of zero charge PL: Photoluminescence RE: Removal efficiency rGO: Reduced graphene oxide ROS: Reactive Oxygen Species SE: Secondary electron SEM: Scanning electron microscope SHE: Standard hydrogen electrode UV-Vis DRS: UV–Vis Diffuse Reflectance Spectroscopy VB: Valance band WWTPs: Wastewater treatment plants XRD: X-ray Diffraction iv Figure 4.19 Pseudo-second-order kinetic model for CIP-photodegradation by MgFe2O4/WO3/rGO nanocomposite 4.2.4 Radical scavengers and proposed mechanism of CIP photodegradation process Ct/Co values obtained when CIP solutions were treated by MgFe2O4/WO3/rGO nanocomposite at the optimal conditions in the presence and absence of t-BuOH (HO• radical scavengers) are presented in Figure 4.20 After the treatment, the Ct/Co values for CIP removal in the absence and in the presence of t-BuOH are 0.09 and 0.45, implying that the CIP removal efficiency were 91% and 55%, respectively Due to the addition of t-BuOH, the efficiency decreases by 36%, which highlights the significance of HO• for CIP degradation process 67 Figure 4.20 Comparison between CIP removal with or without t-BuOH by MgFe2O4/WO3/rGO nanocomposite The proposed mechanism of MgFe 2O4/WO3/rGO are described as follow The mechanism is consistent with those reported in previous studies (Suresh et al., 2021; Vu et al., 2022) Step 1: Light absorption 𝑃ℎ𝑜𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 + ℎ𝑣 → 𝑃ℎ𝑜𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 (𝑒 − + ℎ+ ) Step 2: EVB of WO3 is 3.35 V, which can oxidize H2O and OH- to form hydroxyl radicals 𝐻2 𝑂 + ℎ + → 𝐻 + + 𝐻𝑂 𝑂𝐻 − + ℎ+ → 𝐻𝑂 68 Step 3: ECB of MgFe2O4 is -1.40 V, which can reduce dissolved oxygen to form O2-• 𝑂2 + 𝑒 − → 𝑂2− 𝑂2.− + 𝐻 + → 𝐻𝑂2 2𝐻𝑂2 → 𝐻2 𝑂2 + 𝑂2 𝐻2 𝑂2 + 𝑒 − → 𝐻𝑂 + 𝑂𝐻 − Step 4: Photodegradation of CIP 𝐶𝐼𝑃 + 𝐻𝑂 → 𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 → 𝐶𝑂2 + 𝐻2 𝑂 The addition of rGO can help deal with the fast recombination rate of charged carriers, which has been exhibited by the result from PL analysis The schematic diagram for CIP photodegradation is illustrated in Figure 4.21 Figure 4.21 Proposed mechanism for CIP photodegradation by MgFe 2O4/WO3/rGO nanocomposite 69 4.2.5 Stability and recyclability of MgFe2O4/WO3/rGO nanocomposite Figure 4.22 exhibits the extraction of the MgFe2O4/WO3/rGO nanocomposite by magnet after the CIP photodegradation Figure 4.22 MgFe2O4/WO3/rGO (a) before and (b) after extracted by magnet Ct/Co values obtained when CIP solutions were treated by MgFe2O4/WO3/rGO nanocomposite at the optimal conditions for three cycles are presented in Figure 4.23 Figure 4.23 Stability and recyclability of MgFe2O4/WO3/rGO nanocomposite after three cycles 70 The results in Fig 4.23 showed that, after three cycles, the CIP removal efficiency by the examined catalyst still remained outstanding photocatalytic performance of 84% This suggests that the MgFe2O4/WO3/rGO nanocomposite was durable and effective 71 CHAPTER CONCLUSION AND RECOMMENDATIONS Conclusions MgFe2O4/WO3/rGO nanocomposite was synthesized successfully The XRD and FTIR spectra of MgFe2O4/WO3/rGO nanocomposite displayed all characteristic peaks of pristine MgFe2O4, WO3 and rGO components, implying the successful formation of crystallite structures and characteristic bonds of all nanomaterials without any impurity Additionally, their SEM image and EDX spectra revealed the distribution of MgFe 2O4 and WO3 nanomaterial on the surface of rGO sheet Moreover, Tauc plot exhibited the band-gap energy of MgFe2O4/WO3/rGO nanocomposite at 1.87 eV, implying that MgFe2O4/WO3/rGO nanocomposite work well in the visible-light region Besides, PL spectra indicated that the recombination rate of charge carriers obtained with MgFe2O4/WO3/rGO nanocomposite was lower than that achieved with the pristine components due to the addition of rGO as photogenerated electron trap Optimal conditions for CIP photodegradation by MgFe2O4/WO3/rGO nanocomposite, including initial pH of CIP solution, dosage of photocatalyst, and initial CIP concentration, were determined in this study The highest CIP removal efficiency was found to be 91% when ppm CIP solution was treated by 0.75 g/L MgFe2O4/WO3/rGO nanocomposite at pH within 30 mins in the dark to reach adsorption-desorption equilibrium and subsequent irradiation by 20W white lamp for 180 mins The CIP photocatalysis process followed pseudo-first-order kinetic model, with the rate constant of 0.0098 min-1 Thanks to the addition of t-BuOH (HO• radical scavengers), the significance of HO• for CIP degradation process was highlighted Finally, MgFe2O4/WO3/rGO nanocomposite exhibits durability since after three cycles, the CIP removal efficiency by the examined catalyst still remained outstanding photocatalytic performance of 84% Recommendations All photodegradation experiments in this study were conducted with the synthetic wastewater Hence, further study on CIP removal using the synthesized nanomaterial with the real wastewater is necessary 72 Due to the time limitation and effects of COVID-19 pandemics, this work currently lacks LC-MS-MS analysis to determine the intermediate by-products of CIP photodegradation These tests should be performed in the future to affirm applicability of MgFe2O4/WO3/rGO nanocomposite in the reality This study investigates the technical viability of CIP photodegradation by MgFe2O4/WO3/rGO nanocomposite However, the economic feasibility and environmental impacts of MgFe2O4/WO3/rGO nanocomposite production and application have not yet been studied Therefore, these aspects should be the focuses of the future work 73 REFERENCES Ahmadzadeh, S., Asadipour, A., Pournamdari, M., Behnam, B., Rahimi, H R., & Dolatabadi, M., 2017 Removal of ciprofloxacin from hospital wastewater using electrocoagulation technique by aluminum electrode: optimization and modelling through response surface methodology Process Safety and Environmental Protection, 109, 538-547 Akbari, S., Masoudpanah, S., Mirkazemi, S., & Aliyan, N., 2017 PVA assisted coprecipitation synthesis and characterization of MgFe 2O4 nanoparticles Ceramics International, 43(8), 6263-6267 Alam, S N., Sharma, N., & Kumar, L., 2017 Synthesis of graphene oxide (GO) by modified hummers method and its thermal reduction to obtain reduced graphene oxide (rGO) Graphene, 6(1), 1-18 Ali, N., Idris, N H., Din, M M., Mustafa, N., Sazelee, N., Yap, F H., Sulaiman, N., Yahya, M., & Ismail, M., 2018 Nanolayer-like-shaped MgFe2O4 synthesised via a simple hydrothermal method and its catalytic effect on the hydrogen storage properties of MgH Rsc Advances, 8(28), 15667-15674 Aliyan, N., Mirkazemi, S., Masoudpanah, S., & Akbari, S., 2017 The effect of post-calcination on cation distributions and magnetic properties of the coprecipitated MgFe2O4 nanoparticles Applied Physics A, 123(6), 446 Alonso, J J S., El Kori, N., Melián-Martel, N., & Del Río-Gamero, B., 2018 Removal of ciprofloxacin from seawater by reverse osmosis Journal of environmental management, 217, 337-345 Bai, S., Zuo, Y., Zhang, K., Zhao, Y., Luo, R., Li, D., & Chen, A., 2021 WO3ZnFe2O4 heterojunction and rGO decoration synergistically improve the sensing performance of triethylamine Sensors and Actuators B: Chemical, 347, 130619 Binh, V N., Dang, N., Anh, N T K., & Thai, P K., 2018 Antibiotics in the aquatic environment of Vietnam: sources, concentrations, risk and control strategy Chemosphere, 197, 438-450 Bosch-Navarro, C., Coronado, E., Martí-Gastaldo, C., Sánchez-Royo, J., & Gómez, M G., 2012 Influence of the pH on the synthesis of reduced graphene oxide under hydrothermal conditions Nanoscale, 4(13), 3977-3982 10 Botas, C., Álvarez, P., Blanco, P., Granda, M., Blanco, C., Santamaría, R., Romasanta, L J., Verdejo, R., López-Manchado, M A., & Menéndez, R., 2013 Graphene materials with different structures prepared from the same graphite by the Hummers and Brodie methods Carbon, 65, 156-164 11 Brundle, C R., Wilson, L., Evans, C A., Wilson, S., & Wilson, G., 1992 Encyclopedia of materials characterization: surfaces, interfaces, thin films: Gulf Professional Publishing 74 12 Cadan, F M., Ribeiro, C., & Azevedo, E B., 2021 Improving g-C3N4: WO3 Zscheme photocatalytic performance under visible light by multivariate optimization of g-C3N4 synthesis Applied surface science, 537, 147904 13 Campoli-Richards, D M., Monk, J P., Price, A., Benfield, P., Todd, P A., & Ward, A., 1988 Ciprofloxacin Drugs, 35(4), 373-447 14 Chaudhary, K., Shaheen, N., Zulfiqar, S., Sarwar, M I., Suleman, M., Agboola, P O., Shakir, I., & Warsi, M F., 2020 Binary WO 3-ZnO nanostructures supported rGO ternary nanocomposite for visible light driven photocatalytic degradation of methylene blue Synthetic Metals, 269, 116526 15 Chen, F., Yang, Q., Yao, F., Wang, S., Sun, J., An, H., Yi, K., Wang, Y., Zhou, Y., & Wang, L., 2017 Visible-light photocatalytic degradation of multiple antibiotics by AgI nanoparticle-sensitized Bi5O7I microspheres: Enhanced interfacial charge transfer based on Z-scheme heterojunctions Journal of catalysis, 352, 160-170 16 Chen, M., Dai, Y., Guo, J., Yang, H., Liu, D., & Zhai, Y., 2019 Solvothermal synthesis of biochar@ ZnFe2O4/BiOBr Z-scheme heterojunction for efficient photocatalytic ciprofloxacin degradation under visible light Applied surface science, 493, 1361-1367 17 Chen, Q., Rondinone, A J., Chakoumakos, B C., & Zhang, Z J., 1999 Synthesis of superparamagnetic MgFe2O4 nanoparticles by coprecipitation Journal of Magnetism and Magnetic Materials, 194(1-3), 1-7 18 Choi, K.-J., Kim, S.-G., & Kim, S.-H., 2008 Removal of antibiotics by coagulation and granular activated carbon filtration Journal of hazardous materials, 151(1), 38-43 19 Chua, C K., & Pumera, M., 2016 The reduction of graphene oxide with hydrazine: elucidating its reductive capability based on a reaction-model approach Chemical Communications, 52(1), 72-75 20 Costa, L N., Nobre, F X., Lobo, A O., & de Matos, J M E., 2021 Photodegradation of ciprofloxacin using Z-scheme TiO2/SnO2 nanostructures as photocatalyst Environmental Nanotechnology, Monitoring & Management, 16, 100466 21 Dozzi, M V., Marzorati, S., Longhi, M., Coduri, M., Artiglia, L., & Selli, E., 2016 Photocatalytic activity of TiO2-WO3 mixed oxides in relation to electron transfer efficiency Applied Catalysis B: Environmental, 186, 157-165 22 Dutta, V., Sharma, S., Raizada, P., Thakur, V K., Khan, A A P., Saini, V., Asiri, A M., & Singh, P., 2021 An overview on WO based photocatalyst for environmental remediation Journal of Environmental Chemical Engineering, 9(1), 105018 23 El-Shafey, E.-S I., Al-Lawati, H., & Al-Sumri, A S., 2012 Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets Journal of Environmental Sciences, 24(9), 1579-1586 75 24 Eticha, T., Kahsay, G., Asefa, F., Hailu, T., Gebretsadik, H., Gebretsadikan, T., & Thangabalan, B., 2018 Chemometric-Assisted spectrophotometric method for the simultaneous determination of ciprofloxacin and doxycycline hyclate in pharmaceutical formulations Journal of analytical methods in chemistry, 2018 25 Feng, X., Wang, P., Hou, J., Qian, J., Ao, Y., & Wang, C., 2018 Significantly enhanced visible light photocatalytic efficiency of phosphorus doped TiO with surface oxygen vacancies for ciprofloxacin degradation: Synergistic effect and intermediates analysis Journal of hazardous materials, 351, 196-205 26 Garcia-Muñoz, P., Fresno, F., Víctor, A., & Keller, N., 2020 Ferrite materials for photoassisted environmental and solar fuels applications Heterogeneous Photocatalysis, 107-162 27 George, M., Ajeesha, T., Manikandan, A., Anantharaman, A., Jansi, R., Kumar, E R., Slimani, Y., Almessiere, M., & Baykal, A., 2021 Evaluation of Cu– MgFe2O4 spinel nanoparticles for photocatalytic and antimicrobial activates Journal of Physics and Chemistry of Solids, 153, 110010 28 Ghattavi, S., & Nezamzadeh-Ejhieh, A., 2021 A double-Z-scheme ZnO/AgI/WO3 photocatalyst with high visible light activity: experimental design and mechanism pathway in the degradation of methylene blue Journal of Molecular Liquids, 322, 114563 29 Grewal, A., Patro, S., Kanungo, S., & Bhardwaj, S., 2012 Simultaneous spectrophotometric estimation of ciprofloxacin and ornidazole in tablet dosage form International Journal Of Pharmaceutical Sciences and Research, 3(8), 2716 30 Guo, H.-L., Wang, X.-F., Qian, Q.-Y., Wang, F.-B., & Xia, X.-H., 2009 A green approach to the synthesis of graphene nanosheets ACS nano, 3(9), 2653-2659 31 Guo, H., Li, Z., Xiang, L., Jiang, N., Zhang, Y., Wang, H., & Li, J., 2021 Efficient removal of antibiotic thiamphenicol by pulsed discharge plasma coupled with complex catalysis using graphene-WO3-Fe3O4 nanocomposites Journal of hazardous materials, 403, 123673 32 Habte, A T., & Ayele, D W., 2019 Synthesis and characterization of reduced graphene oxide (rGO) started from graphene oxide (GO) using the tour method with different parameters Advances in Materials Science and Engineering, 2019 33 Harris, D 2015 Quantitative Chemical Analysis th Ed., publ In: WH Freeman 34 Hu, X., Hu, X., Peng, Q., Zhou, L., Tan, X., Jiang, L., Tang, C., Wang, H., Liu, S., & Wang, Y., 2019 Mechanisms underlying the photocatalytic degradation pathway of ciprofloxacin with heterogeneous TiO Chemical Engineering Journal, 380, 122366 35 Hunyadi, D., Sajó, I., & Szilágyi, I M., 2014 Structure and thermal decomposition of ammonium metatungstate Journal of thermal analysis and calorimetry, 116(1), 329-337 76 36 Hwa, K.-Y., Ganguly, A., & Tata, S K S., 2020 Influence of temperature variation on spinel-structure MgFe2O4 anchored on reduced graphene oxide for electrochemical detection of 4-cyanophenol Microchimica Acta, 187(11), 1-13 37 Jakhar, R., Yap, J E., & Joshi, R., 2020 Microwave reduction of graphene oxide Carbon, 170, 277-293 38 Jalil, M E R., Baschini, M., & Sapag, K., 2015 Influence of pH and antibiotic solubility on the removal of ciprofloxacin from aqueous media using montmorillonite Applied Clay Science, 114, 69-76 39 Kefeni, K K., Mamba, B B., & Msagati, T A., 2017 Application of spinel ferrite nanoparticles in water and wastewater treatment: a review Separation and Purification Technology, 188, 399-422 40 Kohli, R., & Mittal, K L., 2011 Developments in surface contamination and cleaning, Volume 4: Detection, characterization, and analysis of contaminants 41 Kolpin, D W., Furlong, E T., Meyer, M T., Thurman, E M., Zaugg, S D., Barber, L B., & Buxton, H T., 2002 Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999− 2000: A national reconnaissance Environmental science & technology, 36(6), 1202-1211 42 Kosmulski, M., 2021 The pH dependent surface charging and points of zero charge IX Update Advances in Colloid and Interface Science, 296, 102519 43 Kümmerer, K., 2009a Antibiotics in the aquatic environment – A review–Part II Chemosphere, 75(4), 435-441 44 Kümmerer, K., 2009b Antibiotics in the aquatic environment – A review – Part I Chemosphere, 75(4), 417-434 45 Kurian, J., & Mathew, M J., 2017 A facile approach to the elucidation of magnetic parameters of CuFe 2O4 nanoparticles synthesized by hydrothermal route Journal of Magnetism and Magnetic Materials, 428, 204-212 46 Le, T X., & Munekage, Y., 2004 Residues of selected antibiotics in water and mud from shrimp ponds in mangrove areas in Viet Nam Marine pollution bulletin, 49(11-12), 922-929 47 Li, K., Yediler, A., Yang, M., Schulte-Hostede, S., & Wong, M H., 2008 Ozonation of oxytetracycline and toxicological assessment of its oxidation byproducts Chemosphere, 72(3), 473-478 48 Liang, Y., Yang, Y., Zou, C., Xu, K., Luo, X., Luo, T., Li, J., Yang, Q., Shi, P., & Yuan, C., 2019 2D ultra-thin WO3 nanosheets with dominant {002} crystal facets for high-performance xylene sensing and methyl orange photocatalytic degradation Journal of Alloys and Compounds, 783, 848-854 49 Lien, L T Q., Hoa, N Q., Chuc, N T K., Thoa, N T M., Phuc, H D., Diwan, V., Dat, N T., Tamhankar, A J., & Lundborg, C S., 2016 Antibiotics in wastewater of a rural and an urban hospital before and after wastewater treatment, and the relationship with antibiotic use—a one year study from Vietnam International Journal of Environmental Research and Public Health, 13(6), 588 77 50 Low, J., Jiang, C., Cheng, B., Wageh, S., Al‐Ghamdi, A A., & Yu, J., 2017 A review of direct Z‐scheme photocatalysts Small Methods, 1(5), 1700080 51 Mahdi, M H., Mohammed, T J., & Al-Najar, J A (2021) Advanced Oxidation Processes (AOPs) for treatment of antibiotics in wastewater: A review Paper presented at the IOP Conference Series: Earth and Environmental Science 52 Makuła, P., Pacia, M., & Macyk, W 2018 How to correctly determine the band gap energy of modified semiconductor photocatalysts based on UV–Vis spectra In (Vol 9, pp 6814-6817): ACS Publications 53 Malakootian, M., Nasiri, A., Asadipour, A., & Kargar, E., 2019 Facile and green synthesis of ZnFe2O4@ CMC as a new magnetic nanophotocatalyst for ciprofloxacin degradation from aqueous media Process Safety and Environmental Protection, 129, 138-151 54 Manaia, C M., Novo, A., Coelho, B., & Nunes, O C., 2010 Ciprofloxacin resistance in domestic wastewater treatment plants Water, Air, and Soil Pollution, 208(1), 335-343 55 Mao, D., Yan, X., Wang, H., Shen, Z., & Yi, C., 2021 Catalysis of rGO-WO3 nanocomposite for aqueous bisphenol A degradation in dielectric barrier discharge plasma oxidation process Chemosphere, 262, 128073 56 Mao, J., Zhang, Q., Li, P., Zhang, L., & Zhang, W., 2018 Geometric architecture design of ternary composites based on dispersive WO nanowires for enhanced visible-light-driven activity of refractory pollutant degradation Chemical Engineering Journal, 334, 2568-2578 57 Mei, X., Meng, X., & Wu, F., 2015 Hydrothermal method for the production of reduced graphene oxide Physica E: Low-dimensional Systems and Nanostructures, 68, 81-86 58 Mekhamer, W., & Al-Tamimi, S., 2019 Removal of ciprofloxacin from simulated wastewater by pomegranate peels Environmental Science and Pollution Research, 26(3), 2297-2304 59 Mmelesi, O K., Masunga, N., Kuvarega, A., Nkambule, T T., Mamba, B B., & Kefeni, K K., 2020 Cobalt ferrite nanoparticles and nanocomposites: Photocatalytic, antimicrobial activity and toxicity in water treatment Materials Science in Semiconductor Processing, 105523 60 Naaz, F., Dubey, H K., Kumari, C., & Lahiri, P., 2020 Structural and magnetic properties of MgFe2O4 nanopowder synthesized via co-precipitation route SN Applied Sciences, 2(5), 1-8 61 Nasiruddin Khan, M., & Sarwar, A., 2007 Determination of points of zero charge of natural and treated adsorbents Surface Review and Letters, 14(03), 461-469 62 Nasrollahzadeh, M., Sajjadi, M., Iravani, S., & Varma, R S., 2020 Carbon-based sustainable nanomaterials for water treatment: State-of-art and future perspectives Chemosphere, 128005 78 63 Nguyen, L T., Nguyen, H T., Pham, T.-D., Tran, T D., Chu, H T., Dang, H T., Nguyen, V.-H., Nguyen, K M., Pham, T T., & Van der Bruggen, B., 2020 UV– visible light driven photocatalytic degradation of ciprofloxacin by N, S co-doped TiO2: the effect of operational parameters Topics in Catalysis, 63(11), 985-995 64 Nguyen, T.-T., Bui, X.-T., Luu, V.-P., Nguyen, P.-D., Guo, W., & Ngo, H.-H., 2017 Removal of antibiotics in sponge membrane bioreactors treating hospital wastewater: Comparison between hollow fiber and flat sheet membrane systems Bioresource Technology, 240, 42-49 65 Nidheesh, P V., 2017 Graphene-based materials supported advanced oxidation processes for water and wastewater treatment: a review Environmental Science and Pollution Research, 24(35), 27047-27069 66 Paula, L F., Hofer, M., Lacerda, V P., Bahnemann, D W., & Patrocinio, A O T., 2019 Unraveling the photocatalytic properties of TiO 2/WO3 mixed oxides Photochemical & Photobiological Sciences, 18(10), 2469-2483 67 Pawliszyn, J., 2012 Comprehensive sampling and sample preparation: Analytical techniques for scientists: Academic Press 68 Peleyeju, M G., & Viljoen, E L., 2021 WO 3-based catalysts for photocatalytic and photoelectrocatalytic removal of organic pollutants from water–A review Journal of Water Process Engineering, 40, 101930 69 Poh, H L., Šaněk, F., Ambrosi, A., Zhao, G., Sofer, Z., & Pumera, M., 2012 Graphenes prepared by Staudenmaier, Hofmann and Hummers methods with consequent thermal exfoliation exhibit very different electrochemical properties Nanoscale, 4(11), 3515-3522 70 Qin, H., He, Y., Xu, P., Huang, D., Wang, Z., Wang, H., Wang, Z., Zhao, Y., Tian, Q., & Wang, C., 2021 Spinel ferrites (MFe 2O4): Synthesis, improvement and catalytic application in environment and energy field Advances in Colloid and Interface Science, 102486 71 Reichelt, R 2007 Science of Microscopy, chapter Scanning Electron Microscopy, edited by: HAWKES, PW and SPENCE, JCH In: Springer Science+ Bussines Media, LLC, New York 72 Ren, B., Huang, Y., Han, C., Nadagouda, M N., & Dionysiou, D D., 2016 Ferrites as photocatalysts for water splitting and degradation of contaminants In Ferrites and Ferrates: Chemistry and Applications in Sustainable Energy and Environmental Remediation (pp 79-112): ACS Publications 73 Riboni, F., Bettini, L G., Bahnemann, D W., & Selli, E., 2013 WO 3–TiO2 vs TiO2 photocatalysts: effect of the W precursor and amount on the photocatalytic activity of mixed oxides Catalysis Today, 209, 28-34 74 Rimoldi, L., Giordana, A., Cerrato, G., Falletta, E., & Meroni, D., 2019 Insights on the photocatalytic degradation processes supported by TiO 2/WO3 systems The case of ethanol and tetracycline Catalysis Today, 328, 210-215 79 75 Schneider, J T., Firak, D S., Ribeiro, R R., & Peralta-Zamora, P., 2020 Use of scavenger agents in heterogeneous photocatalysis: truths, half-truths, and misinterpretations Physical Chemistry Chemical Physics, 22(27), 15723-15733 76 Sharma, G., Thakur, B., Kumar, A., Sharma, S., Naushad, M., & Stadler, F J., 2020 Gum acacia‐cl‐poly (acrylamide)@ carbon nitride nanocomposite hydrogel for adsorption of ciprofloxacin and its sustained release in artificial ocular solution Macromolecular Materials and Engineering, 305(9), 2000274 77 Sharma, P C., Jain, A., Jain, S., Pahwa, R., & Yar, M S., 2010 Ciprofloxacin: review on developments in synthetic, analytical, and medicinal aspects Journal of enzyme inhibition and medicinal chemistry, 25(4), 577-589 78 Sharma, R., Bansal, S., & Singhal, S., 2015 Tailoring the photo-Fenton activity of spinel ferrites (MFe2O4) by incorporating different cations (M= Cu, Zn, Ni and Co) in the structure Rsc Advances, 5(8), 6006-6018 79 Skoog, D A., West, D M., Holler, F J., & Crouch, S R., 2013 Fundamentals of analytical chemistry: Cengage learning 80 Suresh, R., Rajendran, S., Kumar, P S., Vo, D.-V N., & Cornejo-Ponce, L., 2021 Recent advancements of spinel ferrite based binary nanocomposite photocatalysts in wastewater treatment Chemosphere, 274, 129734 81 Takasu, H., Suzuki, S., Reungsang, A., & Viet, P H., 2009 Fluoroquinolone (FQ) contamination does not correlate with occurrence of FQ-resistant bacteria in aquatic environments of Vietnam and Thailand Microbes and environments, 1103080279-1103080279 82 Tamaddon, F., Nasiri, A., & Yazdanpanah, G., 2020 Photocatalytic degradation of ciprofloxacin using CuFe2O4@ methyl cellulose based magnetic nanobiocomposite MethodsX, 7, 100764 83 Tasca, A L., Clematis, D., Stefanelli, E., Panizza, M., & Puccini, M., 2020 Ciprofloxacin removal: BDD anode coupled with solid polymer electrolyte and ultrasound irradiation Journal of Water Process Engineering, 33, 101074 84 Tran, C V., Quang, D V., Nguyen Thi, H P., Truong, T N., & La, D D., 2020 Effective removal of Pb (II) from aqueous media by a new design of Cu–Mg binary ferrite Acs Omega, 5(13), 7298-7306 85 Tran, D T., 2020 rGO/persulfate metal-free catalytic system for the degradation of tetracycline: effect of reaction parameters Materials Research Express, 7(7), 075501 86 Van Tran, C., La, D D., Hoai, P N T., Ninh, H D., Hong, P N T., Vu, T H T., Nadda, A K., Nguyen, X C., Nguyen, D D., & Ngo, H H., 2021 New TiO2doped Cu–Mg spinel-ferrite-based photocatalyst for degrading highly toxic rhodamine B dye in wastewater Journal of hazardous materials, 420, 126636 87 Van Tran, T., Nguyen, D T C., Le, H T., Tu, T T., Le, N D., Lim, K T., Bach, L G., & Nguyen, T D., 2019 MIL-53 (Fe)-directed synthesis of hierarchically 80 mesoporous carbon and its utilization for ciprofloxacin antibiotic remediation Journal of Environmental Chemical Engineering, 7(1), 102881 88 Vasudevan, V., Thangavel, S., Nallamuthu, G., Kirubakaran, K., Ramasubramanian, P A., & Venugopal, G., 2018 Enhanced photocatalytic properties of nanostructured WO3 semiconductor-photocatalyst prepared via hydrothermal method Journal of nanoscience and nanotechnology, 18(5), 33203328 89 Vu, T.-P.-T., Tran, D.-T., & Dang, V.-C., 2022 Novel N, C, S-TiO2/WO3/rGO Z-scheme heterojunction with enhanced visible-light driven photocatalytic performance Journal of Colloid and Interface Science, 610, 49-60 90 Wajahat, R., Yasar, A., Khan, A M., Tabinda, A B., & Bhatti, S G., 2019 Ozonation and photo-driven oxidation of ciprofloxacin in pharmaceutical wastewater: degradation kinetics and energy requirements Polish Journal of Environmental Studies, 28(3), 1-6 91 Wang, J., Salihi, E C., & Šiller, L., 2017 Green reduction of graphene oxide using alanine Materials Science and Engineering: C, 72, 1-6 92 Wang, X., & Chen, X., 2018 Novel nanomaterials for biomedical, environmental and energy applications: Elsevier 93 Weston, D., 1996 Environmental considerations in the use of antibacterial drugs in aquaculture 94 Yang, Z.-z., Zheng, Q.-b., Qiu, H.-x., Jing, L., & Yang, J.-h., 2015 A simple method for the reduction of graphene oxide by sodium borohydride with CaCl2 as a catalyst New Carbon Materials, 30(1), 41-47 95 Yao, B., Luo, Z., Du, S., Yang, J., Zhi, D., & Zhou, Y., 2021 Sustainable biochar/MgFe2O4 adsorbent for levofloxacin removal: Adsorption performances and mechanisms Bioresource Technology, 340, 125698 96 Yu, R., Zhao, J., Zhao, Z., & Cui, F., 2019 Copper substituted zinc ferrite with abundant oxygen vacancies for enhanced ciprofloxacin degradation via peroxymonosulfate activation Journal of hazardous materials, 390, 121998 97 Zaaba, N., Foo, K., Hashim, U., Tan, S., Liu, W.-W., & Voon, C., 2017 Synthesis of graphene oxide using modified hummers method: solvent influence Procedia engineering, 184, 469-477 98 Zhang, G.-F., Liu, X., Zhang, S., Pan, B., & Liu, M.-L., 2018a Ciprofloxacin derivatives and their antibacterial activities European Journal of Medicinal Chemistry, 146, 599-612 99 Zhang, J., Tian, B., Wang, L., Xing, M., & Lei, J., 2018b Mechanism of photocatalysis In Photocatalysis (pp 1-15): Springer 81