Titanium dioxide doping zinc ferrite with enhanced ultraviolet and visible light photoacrivity for methyl orange degradation

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURAL AND FORESTRY DUONG THI NGOC ANH TITANIUM DIOXIDE DOPING ZINC FERRITE WITH ENHANCED ULTRAVIOLET AND VISIBLE LIGHT PHOTOACTIVITY FOR METHYL ORANGE DEGRADATION BACHELOR THESIS Study Mode : Full-time Major : Environmental Science and Management Faculty : International Training and Development Center Batch : 2011-2015 Thai Nguyen, September 2015 DOCUMENTATION PAGE WITH ABSTRACT Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of environmental Science and Management Student name Duong Thi Ngoc Anh Student ID DTN1153180128 Thesis Title Titanium dioxide doping zinc ferrite with enhanced ultraviolet and visible light photoactivity for methyl orange degradation Supervisors 1, Prof Ruey-an Doong, National Tsing -Hua University, Taiwan 2, Dr Nguyen Thanh Hai, Thai Nguyen University of Agriculture and Forestry, Vietnam Abstract: In this report, zinc ferrite (ZnFe2O4) and Titanium dioxide doping zinc ferrite nanoparticles (TiO2@ZnFe2O4) were prepared by hydrothermal method Ultraviolet – visible (UV-Vis) spectroscopy results show that absorption edge of TiO2@ZnFe2O4 has moved to the visible spectrum range in comparison with the undoped TiO2 and Zinc ferrite doped Titanium dioxide narrows band gap of TiO2 X-ray diffraction (XRD) result point out that zinc ferrite doping titanium dioxide promotes the phase transformation of Titanium dioxide from anatase to rutile and Transmission Electron Microscopy (TEM) result indicated that when TiO2 was doped with ZnFe2O4, it is particle size will decrease with average particle size in the range of 25-30 nm The photocatalytic experimental results indicated that zinc ferrite doped titanium dioxide powders can effectively photodegrade methyl orange under visible light irradiation and ultraviolet irradiation The result also indicated ii that ZnFe2O4 doping TiO2 will enhance the photocatalytic activity of TiO2 Keywords ZnFe2O4, TiO2@ZnFe2O4, hydrothermal, photocatalytic, methyl orange Number of papers 40 Date of submission September 30th, 2015 Supervisor’s signature iii ACKNOWLEDGEMENT Fortunately, I have a precious internship opportunity to learning and professional development in Department of Biomedical Engineering and Environmental Sciences in National Tsing Hua University (NTHU), Taiwan First of all, I want to thanks my supervisors Prof Ruey-An Doong and Dr Nguyen Thanh Hai, who took time out to hear, guide, support and encourage me on the correct path and allowing me to carry out my study to have successful results Especially, their priceless advices are not a small contribution in orienting my careers and future Moreover, I am grateful to Nguyen Thanh Binh (Ph.D) about the help dedicated of his during my studies and research in this laboratory He was hearted guidance, given the comments and the orientation in my experiment steps as well as the process of writing my report I would like to thank Amber, Amy, Judy and Ruby for their guidance to use a variety of important machinery serving my experiment, Rama and Duncan for their help in perform analysis of TEM and XRD samples I would also like to thank all FATECOL members, Biomedical Engineering and Environmental Sciences, National Tsing-Hua University, Taiwan, they going on supports and suggestions Last but not least, thanks to my parents and good friends who always encourage me and offer support and love Sincerely, Duong Thi Ngoc Anh iii TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES LIST OF ABBREVATIONS PART I INTRODUCTION 1.1 Research rationale 1.2 Research objective 1.3 Research question 1.4 Limitation 1.5 Definitions PART II LITERATURE REVIEW 2.1 Overview of Titanium dioxide 2.1.1 Titanium oxidation structures and properties 2.1.2 The photocatalytic activity of TiO2 2.1.3 Increasing the photoactivity of pure TiO2 10 2.2 Overview of Zinc ferrite 11 2.2.1 Ferrite 11 2.2.2 Properties of Zinc Ferrite 12 2.3 Overview of research and application of nanomaterial 12 2.4 Some methods synthesized ZnFe2O4 and TiO2@ZnFe2O4 13 2.4.1 Thermal methods 13 2.4.2 Sol-gel method 14 2.4.3 Co-precipitation methods 14 2.4.4 Hydrothermal methods 15 iv PART III METHODS 15 3.1 Material 15 3.2 Methods 15 3.2.1 Synthesis of Zinc Ferrite nanoparticles 15 3.2.2 Synthesis zinc ferrite doped titanium dioxide P25 17 3.2.3 Photodegradation of methyl orange by TiO2@ZnFe2O4 nanocomposite 19 3.2.4 Characterization 20 PART IV RESULTS 26 4.1 UV-Vis spectra study 26 4.2 Morphology of TiO2@ ZnFe2O4 27 4.3 XRD spectrum 28 4.4 Degradation of methyl orange 29 4.4.1 Degradation of methyl orange under UV light irradiation 29 4.4.2 Degradation of methyl orange under visible light irradiation 32 PART V DISCUSSION AND CONCLUSION 35 5.1 Discussion 35 5.2 Conclusion 36 REFERENCES 37 v LIST OF FIGURES Figure 1.1 Structure of methyl orange dye Figure 2.1 Crystal structures of the forms of titanium dioxide Figure 2.2 Band gaps of selected photocatalyst 11 Figure 3.1 Preparation of Zinc Ferrite by hydrothermal method 16 Figure 3.2 Photograph of ZnFe2O4 nanoparticles after drying 17 Figure 3.3 Preparation of Zinc Ferrite doped Titanium Dioxide via hydrothermal method 18 Figure 3.4 TiO2@ ZnFe2O4 nanoparticles after drying 19 Figure 3.5 Calibration curve of methyl orange at 465 nm 20 Figure 3.6 Schematic diagram of transmission electron microscope 21 Figure 3.7 The process TEM characterization 22 Figure 3.8 Schematic diagram of ultraviolet-visible spectrometer 23 Figure 4.1 UV-Vis spectra of pure ZnFe2O4, TiO2@ ZnFe2O4 and P25 TiO2 26 Figure 4.2 hν- (hνF(R∞))2 curve of ZnFe2O4 27 Figure 4.3 TEM images of TiO2@ ZnFe2O4 nanocomposite 28 Figure 4.4 XRD patterns of pure ZnFe2O4, TiO2@ ZnFe2O4 and P25- TiO2 29 Figure 4.5 Photocatalytic degradation of MO by P25- TiO2 under UV light 30 Figure 4.6 Photocatalytic degradation of MO by TiO2@ZnFe2O4 under UV light 30 Figure 4.7 The effect of spinel ferrite on the degradation of methyl orange under ultraviolet light irradiation (PH=7) 31 Figure 4.8 Photocatalytic degradation of MO by P25- TiO2 under visible light 32 Figure 4.9 Photocatalytic degradation of MO by TiO2@ZnFe2O4 under visible light 33 Figure 4.10 The effect of spinel ferrite on the degradation of methyl orange under visible light irradiation (λ = 465 nm) 34 LIST OF TABLES Table 4.1 P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange (PH =7) 31 Table 4.2 P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange (PH =7) 33 LIST OF ABBREVATIONS Abbreviations Full text content XRD X-Ray Diffraction TEM Transmission electron microscopy MO Methyl orange UV Ultra-violet Vis Visible EHP Electron-hole pairs NHE Normal hydrogen electrode PART IV RESULTS 4.1 UV-Vis spectra study Figure 4.1 presented UV-Vis spectra of pure ZnFe2O4, TiO2@ ZnFe2O4 and P25 TiO2 It can be seen that the reflectance curves for TiO2@ZnFe2O4 composite powder were between those for pure titanium oxide and pure zinc ferrite, the reflectance in the visible range of 400- 700 nm decreased dramatically This result demonstrated that, upon addition of ZnFe2O4 particles to TiO2, the absorption of the composite powder in the visible spectrum range increased appreciably in comparison with that of the undoped TiO2 This means that the composite powders were sensitive to visible light Reflectance (%) 100 P25 80 P25@ZnFe2O4 60 ZnFe2O4 40 20 200 300 400 500 600 700 800 Wavelength (nm) Figure 4.1 UV-Vis spectra of pure ZnFe2O4, TiO2@ ZnFe2O4 and P25 TiO2 Band gap of materials was determined by using Tauc plots Figure 4.2 shown the curve 26 that plots the value of (hν- (hνF(R∞))2) and the respective tangent (based on the procedure for determining the band gap by using Tauc plot (Tauc, Grigorovici & Vancu 1966)) of pure ZnFe2O4 Figure 4.2 hν- (hνF(R∞))2 curve of ZnFe2O4 In general, band gap of ZnFe2O4 is 2.2 eV, it was smaller than band gap of P25 TiO2 That mean, TiO2@ZnFe2O4 had the ability to absorb visible light as well as improving the photocatalytic efficiency in using UV light case 4.2 Morphology of TiO2@ ZnFe2O4 The morphological study of nanoparticles had been done by transmission electron microscopy (TEM) Figure 4.3 presented the TEM images of TiO2@ ZnFe2O4 27 nanocomposite The TEM images revealed an almost spherical form with average particle size in the range of 25-30 nm as show in figure 4.4 Figure 4.3 TEM images of TiO2@ ZnFe2O4 nanocomposite: a) 50nm,b) 10 nm 4.3 XRD spectrum X-ray diffraction patterns of pure ZnFe2O4, TiO2@ ZnFe2O4 and pure TiO2 P25 were show in figure 4.4 The pure ZnFe2O4 presented in spinel structure and the main diffraction peaks at 2θ were respectively as 29.7º, 35.05º and 62.8º While the pure TiO2 presented in the mixed phased of anatase and rutile in tetragonal structure The main diffraction peaks of anatase phase at 2θ were respectively as 25.05º and 48º, the main diffraction peaks of rutile phase at 2θ were correspondingly as 27.5º, 36.7º and 56º The XRD pattern of TiO2@ZnFe2O4 displayed characteristic diffraction peak of both ZnFe2O4 and TiO2 crystalline phases This result point out that ZnFe2O4 doped TiO2 promotes the phase transformation of TiO2 from anatase to rutile 28 CPS (a.u.) P25@ZnFe2O4 P25 ZnFe2O4 Anatase Rutile ZnFe2O4 20 30 40 50 60 70 80 2θ Figure 4.4 XRD patterns of pure ZnFe2O4, TiO2@ ZnFe2O4 and P25- TiO2 4.4 Degradation of methyl orange 4.4.1 Degradation of methyl orange under UV light irradiation Figure 4.5 and 4.6 illustrated photocatalytic degradation of MO by P25- TiO2 and TiO2@ZnFe2O4 29 Figure 4.5 Photocatalytic degradation of MO by P25- TiO2 under UV light (A: Methyl orange, Irradiation time: B = hr, C =7 hr D = hr) Figure 4.6 Photocatalytic degradation of MO by TiO2@ZnFe2O4 under UV light (A: Methyl orange, Irradiation time: B = hr, C =7 hr D = hr) Figure 4.7 presented the effect of TiO2@ ZnFe2O4 and P25-TiO2 photocatalyst for the degradation of MO under UV light irradiation, respectively and table 4.1 indicated the results of P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange 30 1.0 0.8 C/Co 0.6 0.4 P25 P25@ZnFe2O4 0.2 No catalyst 0.0 Irradiation time (hour) Figure 4.7 The effect of spinel ferrite on the degradation of methyl orange under ultraviolet light irradiation (PH=7) Table 4.1 P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange (PH =7) Photocatalyst Dye(mg/L) Catalyst Wavelength Irradiation Degradation (g/L) time(min) (%) (nm) P25-TiO2 10 365 480 85 TiO2/ZnFe2O4 10 365 480 90 Under UV light irradiation, the photocatalytic degradation of methyl orange proceeded on the TiO2@ ZnFe2O4 photocatalysts After 8h, photodegradation reaction excited by UV light, 90% methyl orange were destroyed on the TiO2@ ZnFe2O4 sample, while 31 85% methyl orange were degraded on the pure P25-TiO2 This result indicated that the removal efficiency of methyl orange with TiO2@ZnFe2O4 was higher than P25-TiO2 That mean ZnFe2O4 doped can improve the photocatalytic activity of TiO2 for methyl orange degradation 4.4.2 Degradation of methyl orange under visible light irradiation Figure 4.8 and 4.9 showed the photocatalytic degradation of MO preceded on the P25TiO2 and TiO2 @ (ZnFe2O4) photocatalyst under visible light irradiation Figure 4.8 Photocatalytic degradation of MO by P25- TiO2 under visible light (A: Methyl orange, Irradiation time: B =1hr, C = 2hr, D = hr, E = 4hr, F = 5hr) 32 Figure 4.9 Photocatalytic degradation of MO by TiO2@ZnFe2O4 under visible light (A: Methyl orange, Irradiation time: B =1hr, C = 2hr, D = hr, E = 4hr, F = 5hr) Figure 4.10 presented the effect of spinel ferrite on the the degradation of methyl orange under visible light irradiation (λ = 465 nm) and table 4.2 showed the results of P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange Table 4.2 P25-TiO2 and TiO2@ZnFe2O4 reacted with methyl orange (PH =7) Photocatalyst Dye Catalyst (mg/L) (g/L) Wavelength Irradiation time Degradation (nm) (min) (%) P25-TiO2 10 465 300 TiO2@ZnFe2O4 10 465 300 30 33 1.0 C/Co 0.9 0.8 P25 P25@ZnFe2O4 0.7 No catalyst 0.6 Irradiation time (hour) Figure 4.10 The effect of spinel ferrite on the degradation of methyl orange under visible light irradiation (λ = 465 nm) After 5h photodegradation reaction excited by visible light, 30% methyl orange were destroyed on the TiO @ (ZnFe2O4) samples, while only a slight degrade methyl orange were occurred on pure TiO samples The degradation of methyl orange on pure TiO2 under visible light irradiation was attributed to the photosensitization process 34 PART V DISCUSSION AND CONCLUSION 5.1 Discussion To summary, the study has developed TiO2@ZnFe2O4 nanocomposite of the potential for waste water purification through utilization of solar energy In this study, ZnFe2O4 and TiO2@ZnFe2O4 were synthesized by hydrothermal method with the aim of extending the light absorption spectrum toward the visible light Their characteristic was evaluated by TEM, XRD and UV-Vis spectroscopy This result indicated that ZnFe2O4 doping could decrease the particle size of TiO2 nanoparticles and promoted the phase transformation of TiO2 from anatase to rutile The UV-Vis spectroscopy analysis was helped calculate band gap of TiO2 and it also show that the absorption of TiO2@ZnFe2O4 has moved to the visible spectrum Band gap of TiO2@ZnFe2O4 was smaller than band gap of pure TiO2 this demonstrates that ZnFe2O4 doping helped shrink the band gap of pure TiO2 This indicated why TiO2 can absorb visible light ZnFe2O4 doping TiO2 would enhance the photocatalytic activity of TiO2 and that ZnFe2O4 doped TiO2 in the coexistence of anatase and rutile has higher efficiency for the degradation of Methyl Orange than that in the anatase phase alone Experimental results obtained in this study clearly demonstrate that TiO2@ZnFe2O4 nanocomposite was an effective adsorbent for organic pollutant in water The photocatalytic degradation of methyl orange indicates that TiO2@ZnFe2O4 powders can effectively photodegrade methyl orange under visible light irradiation and UV light The maximum degradation of methyl orange under UV irradiation is 90% The photoactivity of TiO2@ZnFe2O4 was higher than photocatalytic of pure TiO2 This 35 study provided information about characteristic of Titanium dioxide doping Zinc ferrite, and the results are expected to supply a reference for remove experiments other toxic chemicals in water 5.2 Conclusion In conclusion, the results of TEM, XRD and UV-Vis spectrum showed that when TiO2 was doped with ZnFe2O4, its particle size was decrease; its crystal structure could transformation from anatase to rutile and adsorbs the visible light Experimental results obtained in this study clearly indicate that TiO2@ZnFe2O4 was effective in photocatalytic degradation methyl orange under visible light irradiation and UV light and it also demonstrate that TiO2@ZnFe2O4 nanocomposite was an effective adsorbent for organic pollutant in water This finding is interest and can be extended to remove other toxic chemicals in waters In this report, ZnFe2O4 and TiO2@ZnFe2O4 were synthesized by hydrothermal method The present studies are extended to be other methods to reduce the time of experiment The experiment photocatalysis of TiO 2@ZnFe2O4 for the degradation 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Anh Student ID DTN1153180128 Thesis Title Titanium dioxide doping zinc ferrite with enhanced ultraviolet and visible light photoactivity for methyl orange degradation Supervisors 1, Prof Ruey-an... Titanium dioxide doping zinc ferrite with enhanced ultraviolet and visible light photoactivity for methyl orange degradation" 1.2 Research objective The primary objective of the study is synthesis and. .. 28 4.4 Degradation of methyl orange 29 4.4.1 Degradation of methyl orange under UV light irradiation 29 4.4.2 Degradation of methyl orange under visible light irradiation