(Luận văn thạc sĩ) photocatalytic degradation of methyl orange using ferrite doped titanium dioxide

THAI NGUYEN UNIVERSITY THAI NGUYEN UNIVERSITY OF AGRICULTURE AND FORESTRY NGUYEN THUY GIANG TOPIC TITLE: PHOTOCATALYTIC DEGRADATION OF METHYL ORANGE USING FERRITE DOPED TITANIUM DIOXIDE BACHELOR THESIS Study Mode: Full-time Major : Environmental Science and Management Faculty : International Training and Development Center Batch : 2011 - 2015 Thai Nguyen, 30/09/2015 n THAI NGUYEN UNIVERSITY THAI NGUYEN UNIVERSITY OF AGRICULTURE AND FORESTRY -NGUYEN THUY GIANG TOPIC TITLE: PHOTOCATALYTIC DEGRADATION OF METHYL ORANGE USING FERRITE DOPED TITANIUM DIOXIDE BACHELOR THESIS Study Mode: Full-time Major : Environmental Science and Management Class : K43 – AEP Faculty : International Training and Development Center Batch : 2011 – 2015 Advisor Advisor Prof Ruey-An Doong Assoc Prof Dr Nguyen The Hung Department of Biomedical Department of Environment Engineering and Environmental Thai Nguyen University of Sciences Agriculture and Forestry, Vietnam National Tsing Hua University, Hsinchu, 30013, Taiwan n DOCUMENTATION PAGE WITH ABSTRACT Thai Nguyen University of Agriculture and Forestry Degree program Bachelor of Environmental Science and Management Student name Nguyen Thuy Giang Student ID DTN1153070022 Thesis Title Photocatalytic degradation of Methyl Orange using ferrite doped titanium dioxide Supervisor (s) Prof Ruey-An Doong and Assoc Prof Dr Nguyen The Hung Abstract: Titanium dioxide (TiO2) has high potential to split water into hydrogen and oxygen, and the development of semiconductor photocatalysis using for a wide range of environmental applications Therefore, one of the most significant scientific advance has been the development of visible light active TiO photocatalytic materials In this study, a method of synthesis copper ferrite doped titanium dioxide (P25@CuFe2O4) was conducted to enhance the ability of TiO2 using visible light CuFe2O4 and P25@CuFe2O4 were synthesized by hydrothermal process The composite structure and the presence of the copper ferrite and titanium dioxide phase have been confirmed by TEM, XRD and UVvis spectroscopy P25@CuFe2O4 show good magnetic property, which can get under an external applied magnetic field Photocatalytic ability was examined by degrading methyl orange dye The synthesized P25@CuFe2O4 display the potential of TiO2 photocatalyst under visible irradiation and find the recoverable potential applications in cleaning water pollution with the high magnetic property ii n Keywords Copper ferrite, degradation, photocatalyst, titanium dioxide, visible light Number of pages 43 Date of submission 30/09/2015 iii n ACKNOWLEDGEMENT With deep sense of gratitude, I would like to express my sincere thanks to all those who gave me the possibility to complete thesis work First and foremost, I would like to express my sincere gratitude to my supervisor Prof Ruey-An Doong of National Tsing Hua University, Taiwan, who guided and motivated me to complete my research I would also like to express my thanks to Assoc Prof Dr Nguyen The Hung, the second supervisor, for his support, encouragement throughout my thesis Besides my supervisors, I would like to thank PhD Nguyen Thanh Binh for his valuable, assistant, advices during all my experiments, analysis and writing thesis time I would like to thank PhD Rama Shanker Sahu and Duncan for preparing and characterizing my samples I would also like to thank and all FATECOL members who work in Biomedical Engineering and Environmental Sciences, National Tsing-Hua University, Taiwan, who provided their support, guild and suggestions My sincere thanks also go to Ngoc Anh and Dai for helping me to the end of this study Finally, I would like to express my special thanks and gratitude to my beloved parents, my friends for their love and encourage throughout all the time Thai Nguyen, 30th September, 2015 Student Nguyen Thuy Giang iv n TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES LIST OF ABBREVIATIONS PART I INTRODUCTION .5 1.1 Research rationale .5 1.2 Research’s objective 1.3 Research question .6 1.4 Limitations PART II LITERATURE REVIEW 2.1 Nanotechnology and Nanomaterial 2.1.1 Nanotechnology 2.1.2 Nanomaterial 2.2 Nanocatalysis and Photocatalysis .9 2.2.1 Nanocatalysis 2.2.2 Photocatalysis .11 2.3 Copper ferrite doped P25 Titanium dioxide .12 2.3.1 Semiconductor 12 2.3.2 Titanium dioxide 13 2.3.3 Copper ferrite 17 2.3.4 Copper ferrite doped P25 Titanium dioxide (P25@CuFe2O4) 19 PART III METHODOLOGY 21 3.1 Materials 21 3.1.1 Chemicals 21 v n 3.1.2 Equipment 21 3.1.2.1 Transmission Electron Microscopy 21 3.1.2.2 X-ray diffraction .22 3.1.2.3 UV – Visible spectroscopy .22 3.2 Methods 22 3.2.1 Synthesis of copper ferrite nanoparticles 22 3.2.2 Synthesis of copper ferrite doped P25 titanium dioxide 24 3.2.3 Method of characteristic and morphological measurement 25 3.2.3.1 Transmission Electron Microscopy 25 3.2.3.2 Uv-visible spectroscopy 27 3.2.3.3 X-Ray Diffraction .28 3.2.4 Photocatalytic activity testing 29 PART IV RESULTS AND DISCUSSION 33 4.1 Characterization and morphology of CuFe2O4 and P25@CuFe2O4 33 4.2 Photocatalyst activity 36 4.3 Assessing the ability of methyl orange degradation 37 PART V CONCLUSION AND RECOMMENDATION .40 5.1 Conclusion 40 5.2 Recommendation 41 REFERENCES .42 vi n LIST OF FIGURES Figure 2.1 Expected benefits of nanocatalysis 10 Figure 2.2 Comparison of different electronic band structures of metal, semiconductor and insulator 13 Figure 2.3 Schematic of TiO2 photocatalytic mechanism .16 Figure 2.4 Separation of magnetic nanoparticles using an external magnet (Geukens, 2013) 20 Figure 3.1 Preparation of Copper ferrite nanoparticles .22 Figure 3.2 The sample of copper ferrite powder 23 Figure 3.3 Preparation of Copper ferrite doped P25 Titanium dioxide 24 Figure 3.4 The sample of P25@CuFe2O4 powder .25 Figure 3.5 Schematic of major components for image creation of a typical transmission electron microscopy (TEM) 26 Figure 3.6 A schematic of a double-beam spectrophotometer .27 Figure 3.7 Photoreactor machine 30 Figure 3.8 The resultants of methyl orange after degradation time by using P25@CuFe2O4 with under UV irradiation light (a), visible light (b) 31 Figure 3.9 Standard line for calculation the degradation of methyl orange 32 Figure 4.1 TEM image of P25@CuFe2O4 powders 33 Figure 4.2 XRD pattern of CuFe2O4, P25 TiO2 and P25@CuFe2O4 34 Figure 4.3 Separation of CuFe2O4 (a,b) and P25@CuFe2O4 (c,d) by using external magnet in hexane 35 Figure 4.4 UV-vis reflection spectra for the samples of P25, CuFe 2O4 and P25@CuFe2O4 36 n Figure 4.5 The effect of P25@CuFe2O4 on the degradation of methyl orange under UV light irradiation (λ = 305 nm) 37 Figure 4.6 The effect of P25@CuFe2O4 on the degradation of methyl orange under visible light irradiation (λ = 465 nm) 38 n LIST OF TABLES Table 2.1 Physical and structural properties of anatase and rutile TiO 14 n Where λ is the X-ray wavelength, B is the full width of height maximum (FWHM) of a diffraction peak, θB is the diffraction angle, and K is the Scherrer’s constant of the order of unity for usual crystal However, one should be alerted to the fact that nanoparticles often form twinned structures; therefore, Sherrer’s formula may produce results different from the true particle sizes In addition, X-ray diffraction only provides the collective information of the particle sizes and usually requires a sizable amount of powder It should be noted that since the estimation would work only for very small particles, this technique is very useful in characterizing nanoparticles Similarly, the film thickness of epitaxial and highly textured thin films can also be estimated with XRD 3.2.4 Photocatalytic activity testing Photocatalytic activities of the copper ferrite doped P25 titanium dioxide (P25@CuFe2O4) were evaluated by photocatalytic degradation of Methyl orange (MO) A mixture of MO aqueous solution (20ml) and 20mg of P25@CuFe2O4 was magnetically stirred under dark for 60 minutes to ensure the adsorption equilibrium of MO onto the photocatalyst After that, the first experiment, the mixture was stirred under UV light irradiation (λ = 305 nm) At given time intervals (from hour to hours), 1ml of the suspension was collected and centrifuged to remove photocatalyst particles and analyzed by UV-Vis spectroscopy The second experiment, the mixture was stirred under visible light irradiation (λ = 465 nm) After that, we did the same steps as the first experiment 29 n Figure 3.7 Photoreactor machine To control the irradiation light, we use the photoreactor like in figure 3.7 The results of degradation by using P25@CuFe2O4 under the UV light irradiation and visible light irradiation as the figure 3.8 30 n a b Figure 3.8 The resultants of methyl orange after degradation time by using P25@CuFe2O4 with under UV irradiation light (a), visible light (b) Note: Figure 3.8 (a): A: Initial of Methyl orange, B: after hours, C: after hours, D: after hours Figure 3.8 (b): A: Initial of Methyl orange, B to F: after hours to hours 31 n To analysis the degradation of methyl orange, the first step takes the base samples and measures to draw the standard line as showed in Figure 3.9 2.5 y = 19.897x - 0.0133 R² = 0.9996 Concentration (mg/L) 2.0 1.5 1.0 0.5 0.0 0.00 0.02 0.04 0.06 0.08 0.10 0.12 Abs Figure 3.9 Standard line for calculation the degradation of methyl orange The photocatalytic degradation efficiency of methyl orange dye was calculated by applying the following equation: Degradation % = [(C0 – C)/C0]*100 Where C0 is the initial dye concentration and C is the dye concentration after degradation by copper ferrite dope titanium dioxide 32 n PART IV RESULTS AND DISCUSSION 4.1 Characterization and morphology of CuFe2O4 and P25@CuFe2O4 One important aspect of nanoparticle synthesis is determination of the particle size Figure 4.1 shows the TEM image of P25@CuFe2O4 powders synthesized by hydrothermal reaction between Copper ferrite and P25 Titanium dioxide As seen from Fig 4.1, the size of copper ferrite doped titanium dioxide is less than 50 nm It is clearly to illustrate the composite nature of the particles, consisting of a dark color (CuFe2O4) and gray color (P25 TiO2) The part of CuFe2O4 is laid inside and TiO2 covered outside the CuFe2O4 This TEM image gives an evidence to the success of synthesis copper ferrite doped titanium dioxide with the present of both copper ferrite and titanium dioxide and one importance is the size of powder is belong in nanoscale 50 nm Figure 4.1 TEM image of P25@CuFe2O4 powders 33 n CPS (a.u.) P25@CuFe2O4 P25 CuFe2O4 Anatase Rutile CuFe2O4 20 30 40 50 60 70 80 2θ Figure 4.2 XRD pattern of CuFe2O4, P25 TiO2 and P25@CuFe2O4 The XRD patterns of P25, CuFe2O4 and P25@CuFe2O4 powders are shown in Fig 4.2 P25 TiO2 clearly showed peaks centered at 25.42o, 37.99o, 48.17o, 54.11o and 55.2o with finding anatase and rutile out All the signals of P25 are showed in P25@CuFe2O4, so it means that structure of P25 is not change during the synthesis time of P25@CuFe2O4 Because the ratio of P25:CuFe2O4 is 1:0.1, the present of CuFe2O4 is so small In addition the peaks of CuFe2O4 are nearly the same with peaks of P25, it is harder to identify the amount of CuFe2O4 presented the crystalize structure of P25@CuFe2O4 However, it can be seen in the TEM image that Copper ferrite and P25 are appeared in the final resultant Therefore, it can be apply to degradation of methyl orange dye Magnetic properties of copper ferrite and copper ferrite doped titanium dioxide is also very important properties for reuse of the catalyst 34 n b a c d Figure 4.3 Separation of CuFe2O4 (a,b) and P25@CuFe2O4 (c,d) by using external magnet in hexane From figure 4.3, it is clearly showed that CuFe2O4 and P25@CuFe2O4 have an excellent magnetic property to be separate from the solution This property is high recommend to apply in recycling and reusing the catalyst 35 n 4.2 Photocatalyst activity 100 P25 Reflectance (%) 80 60 40 P25@CuFe2O4 20 CuFe2O4 300 400 500 600 700 800 Wavelength (%) Figure 4.4 UV-vis reflection spectra for the samples of P25, CuFe2O4 and P25@CuFe2O4 Figure 4.4 demonstrated the reflection spectrum of P25 TiO 2, CuFe2O4 and P25@CuFe2O4 in visible light It is shown that P25 TiO2 reflected most of light that is from higher than 80% to nearly 100% It means that it has low ability to absorb the visible light Besides the reflection spectra of CuFe2O4 and P25@ CuFe2O4 are under 20% That demonstrated that the potential of P25@CuFe2O4 can improve the visible light photocatalyst of TiO 36 n 4.3 Assessing the ability of methyl orange degradation The photocatalytic activities of the catalyst were determined by measuring the decrease in the concentration of methyl orange with time in the reaction mixture 1.0 0.8 C/Co 0.6 0.4 P25 0.2 P25@CuFe2O4 No catalyst 0.0 Irradiation time (hour) Figure 4.5 The effect of P25@CuFe2O4 on the degradation of methyl orange under UV light irradiation (λ = 305 nm) Experimental condition: Methyl orange conc = 10 mg/L, catalyst = 1000 mg/L, pH = The photo-degradation curves of methyl orange in the presence of P25 and P25@CuFe2O4 under UV light irradiation in a period of time are shown in figure 4.5 The result indicates that the photocatalytic activity of P25 decreases to approximate 10% of methyl orange concentration in the first hours It is lower 37 n than P25@CuFe2O4 at that time However, after hours until hours, the degradation of P25 is higher than P25@CuFe2O4 reaching at more than 80% and 50% respectively 1.0 C/Co 0.9 0.8 0.7 P25 P25@CuFe2O4 0.6 Irradiation time (hour) Figure 4.6 The effect of P25@CuFe2O4 on the degradation of methyl orange under visible light irradiation (λ = 465 nm) Experimental condition: Methyl orange conc = 10 mg/L, catalyst = 1000 mg/L, pH = The figure 4.6 are shown the photo-degradation curves of methyl orange in the presence of P25 and P25@CuFe2O4 under visible light irradiation in hours The result indicates that the photocatalytic activity of P25 under visible light is zero During the period of time, the photocatalytic activity of copper ferrite doped titanium dioxide decrease to nearly 15% It means that using copper ferrite 38 n doped titanium dioxide has efficiency to degrade the methyl orange dye, although the efficiency is not too high To compare two processes, it is clearly to show that copper ferrite doped titanium dioxide play a good role to utilization of TiO2 using visible light 39 n PART V CONCLUSION AND RECOMMENDATION 5.1 Conclusion In conclusion, the study has synthesized copper ferrite doped titanium dioxide composite for the photocatalytic degradation of methyl orange dye Copper ferrite doped titanium dioxide has good morphology, physical and chemical structure and magnetic properties The main advantages of this material have a simple synthesis, cost effectiveness and ability of recycle In the research, CuFe2O4 and P25@CuFe2O4 have synthesized by hydrothermal method Their characteristic and morphology were analyzed by TEM, XRD and UV-vis spectroscopy The degradation capacity of P25@CuFe2O4 was evaluated by Uv-vis spectroscopy Resultants of P25@CuFe2O4 has excellent properties It is acceptable as nanoparticles with smaller than 50 nm in the size Structure of P25@CuFe2O4 included both copper ferrite and P25 TiO2 In addition, magnetic property of P25@CuFe2O4 is quite high, so it is easily to recovery and reuse Besides, experimental results is clearly demonstrate that P25@CuFe2O4 is effective to degrade for methyl orange with over 60% under UV light irradiation and over 15% under visible light irradiation after hours The results shows that P25@CuFe2O4 can enhance the photocatalytic of TiO2 from using UV light to using visible light 40 n 5.2 Recommendation The ability of degradation methyl orange by using P25@CuFe2O4 is not significant, so we need more time to continue to find what the reason is and how to improve the catalyst to have higher result 41 n REFERENCES Ayyappan, S., Mahadevan, S., Chandramohan, P., Srinivasan, M., Philip, J (2010) Phys Chem (Vol 114, p 6334-6341) Cao, G (2004) Characterization and properties of nanomaterials In Nanostructures and nanomaterials: Synthesis, Properties, and Applications (Chapter 8, p.331) London: Imperial College press Geukens, I., & Vos, D (2013) Recovery of Metallic Nanoparticles In P Serp & K Philippot (Eds.), Nanomaterials in Catalysis (1st ed., Chapter 8, p 321) Singapore: Markono Print Media Pte Ltd Gupta, S M., & Tripathi, M (2011) A review of TiO2 nanoparticles Chinese Science Bulletin,56(16), p 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Singapore: World Scientific Publishing Co Pte Ltd 43 n ... the study has synthesized copper ferrite doped titanium dioxide composite for the photocatalytic degradation of methyl orange dye Copper ferrite doped titanium dioxide has good morphology, physical... During the period of time, the photocatalytic activity of copper ferrite doped titanium dioxide decrease to nearly 15% It means that using copper ferrite 38 n doped titanium dioxide has efficiency... the most useful method is ferrite doping Base on some rationales above; I conducted a research ? ?Photocatalytic degradation of methyl orange using ferrite doped titanium dioxide? ?? 1.2 Research’s