(Luận văn thạc sĩ) 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 h 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 h 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 h 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 h TABLE OF CONTENTS h 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 h 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 h i LIST OF FIGURES h 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 h iii LIST OF ABBREVIATIONS 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 h AOP: 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 h 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 h 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 h 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 h 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 h 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, h 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 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