The use of magnetic nanocomposites in fenton reaction for catalytic degradation of methylene blue

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY KHUONG NAM THAI TOPIC TITLE: THE USE OF MAGNETIC NANOCOMPOSITES IN FENTON REACTION FOR CATALYTIC DEGRADATION OF METHYLENE BLUE BACHELOR THESIS Study mode: Full-time Major: Environmental Science and Management Faculty: International Training and Development Center Batch: 2010-2015 Thai Nguyen, 15/01/2015 i DOCUMENTATION PAGE WITH ABSTRACT Thai Nguyen University of Agriculture and Forestry Degree program Bachelor of Environmental Science and Management Student name Khuong Nam Thai Student ID DTN1053110174 Thesis title The use of magnetic nanocomposite in Fenton reaction for catalytic degradation of methylene blue Supervisor (s) Asoc Prof Huang Yu-Fen1 & Dr Do Thi Ngoc Oanh2 Internship place Department of Biomedical Engineering and Environmental Science, National Tsing Hua University, Taiwan Abstract Oxidation by Fenton-like reactions is proven and economically feasible process for destruction of a variety of hazardous pollutants in wastewater MNPs were synthesis via a thermal decomposition method and Au@FexOy via electrooxidation procedure The synthesis of MNPs and Au@FexOy was characterized by several techniques, Ultraviolet–visible spectroscopy (UV-Vis), and Transmission Electron Microscopy (TEM) The concentrations of dye degradation Department of Biomedical Engineering & Environmental Science, National Tsing Hua University, Taiwan Faculty of Agronomy, Thai Nguyen University of Agriculture and Forestry ii were determined spectrophotometrically using Plate Readers at 665 nm, the absorption maxima of the dye Moreover, in order to apply using magnetic nanocomposties in Fenton reaction for degradation of methylene blue, concentration of Iron ion and hydrogene peroxide must be optimized The magnetic nanocomposites showed good catalytic performance for MB organic dye oxidation by H2O2 after hours of reaction The reaction was able to proceed at pH neutral in room temperature Finally, some future trends and prospective in this research areas are also discussed Keywords Fenton reaction, magnetic nanocomposites , conversion efficiency, spectrophotometrically, methylene blue, H2O2 Number of pages 44 Date of submission 15th January 2015 iii ACKNOWLEDGEMENT I would like firstly to thank Dr Do Thi Ngoc Oanh From the beginning, she had confidence in my abilities to not only complete a degree but to complete it with excellence I wish to thank the members of YF lab, Department of Biomedical Engineering and Environmental Science, National Tsing Hua University, Taiwan for their support, patience and good humor Their gentle but firm direction has been most appreciated Asoc Prof Yu-Fen Huang Supervisor’s interest in sense of competence was the impetus for my project Mr Andy PhD student’s, an extremely exemplary and responsible group leader, was particularly helpful in guiding me toward a qualitative methodology and inspiring me in whole period of internship I would like to give a big acknowledgment to Advantaged Education Program that giving me a great chance in taking this thesis research Especially Dr Duong Van Thao Headteacher’s who is enthusiasm supports me in whole time study Finally I would like to send to my parents and the whole family gratitude and affection iv TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES PART I INTRODUCTION 1.1 Research rationale 1.2 Research’s objective PART II LITERATURE REVIEW 2.1 Nanotechnologies and nanomaterials 2.2 Synthesis of nanonaterials 2.2.1 General principles 2.2.2 Magnetic nanoparticles 2.2.3 Synthesis of gold@iron oxide nanoparticles 10 2.2 Overview of research and application of nanomaterial and nanocomposite 14 2.2.1 Electronic technology and information technology 14 2.2.2 Environmental treatment material 15 2.3 Fenton reaction and its application for degradation of methylene blue 16 2.3.1 Fenton reaction 16 2.3.2 Fenton reaction for degradation of methylene blue 17 2.4 The use of magnetic nanocomposites in Fenton reaction for catalytic degradation of methylene blue 19 2.5 The equipment used to determine the properties of gold nanoparticles and methylene blue degradation 19 v 2.5.1 Ultraviolet–visible spectroscopy (UV-Vis) 19 2.5.2 Transmission Electron Microscopy (TEM) 20 PART III METHODS 23 3.1 Materials 23 3.1.1 Chemicals 23 3.1.2 Equipment 24 3.2 Methods 24 3.2.1 Determine the optimum concentration of Fe2+ 24 3.2.2 Determine the optimum concentration of H2O2 28 3.2.3 Effect of pH value on conversion efficiency of MB 29 3.3.4 Degradation of MB by Iron (II), Iron (III) 30 3.3.5 The use of MNC, Au@FexOy in degradation of MB 31 PART IV RESULTS 33 4.1 Determination the optimum the concentration of Iron (II) for degradation of MB 33 4.2 Determination the optimum concentration of H2O2 for degradation of MB 34 4.3 Effect of pH value on degradation of MB 35 4.4 Degradation of MB by Iron (II), Iron (III) 36 4.5 The use of MNC, Au@FexOy in degradation of dye 37 PART V DISCUSSION AND CONCLUSION 44 5.1 Discussion 44 5.2 Conclusion 44 vi REFERENCES 45 vii LIST OF FIGURES Figure 1.3 TEM images of Fe3O4 NPs in different scale bar: (a) 50 nm; (b) 100 nm 10 Figure 1.4 UV–Vis spectra of AuNP electrooxidation with different time using citrate buffer 12 Figure 1.5 TEM image of a) AuNP( core ± Shell: 48 ± nm); b) Au@Fe xOy at 550 electrooxidation-citrate buffer (core ± Shell: 12 ± nm); c) Au@FexOy at 360 electrooxidation-citrate buffer (core ± Shell: 51 ± 12 nm) and d) Au@FexOy at twice electrooxidation (core ± Shell: 44 ± 21 nm) 13 Figure 1.6 TEM images of a) Au@FexOy and b) Au@FexOy through an annealing process in mM citrate buffer (pH 6.8) with 30 sonication Annealing condition: 350℃, 6h in N2 13 Figure 1.1 Ultraviolet–visible spectroscopy (UV-Vis) 20 Figure 1.2 Schematic diagram of a TEM Generally, TEM is divided into two main parts: illumination and imaging 21 Figure 1.9 Degradation MB by different Fe2+ concentration in 60 minutes, pH = 2-3.5 33 Figure 2.1 Degradation MB by different [H2O2] concentration in 60 minutes, pH = 2-3.5 34 Figure 2.2 Effect of pH on degradation of MB 35 Figure 2.3 Degradation of methylene blue by Fe (II); Fe (II) + Fe (III) and Fe (III) at pH 2.5-3.5 37 Figure 2.4 Degradation of methylene blue by MNC, H2O2 4x and pH = 38 Figure 2.5 Degradation of methylene blue by MNC, H2O2 8.82×10−1 M (200x), pH = with spike at hours 39 Figure 2.6 Degradation of MB by MNC, Au@FexOy after annealing, Au@FexOy before annealing at pH = 7, [H2O2] = 2000x 40 Figure 2.7 Degradation of MB by a) H2O2 + H2O, b) Fe(II), c) Fe(III), d) Fe(II)+Fe(III), e) Au@FexOy after annealing, f) Au@FexOy before annealing and g) MNC (pH = 7) 41 Figure 2.8 Photos of A) degradation of MB by MNC at the beginning, a)-b) at the end of reaction and B) degradation of MB by Fe (II) at the end of reaction with concentration of 200 times dilute fold of H2O2 (pH = 7) after 12 hours 42 LIST OF TABLES Table 1.1 Chemicals used in the experiment 23 Table 1.2 Preparation of Methylene blue stock solution 24 Table 1.3 Preparation stock solution of Fe2+ 25 Table 1.4 Preparation stock solution of H2O2 26 PART IV RESULTS 4.1 Determination the optimum the concentration of Iron (II) for degradation of MB To determine the optimum Iron (II) concentration we used different Iron (II) concentrations as following: treatment 1(Fe 0x, M), treatment (3.58×10−5 M), treatment (1.43×10−4 M), and treatment (2.86×10−4 M) Those concentration have the same concentration base with MB, 3.13×10−5 M and H2O2, 1.76×10−3 M, respectively The pH was adjusted from 23.5 by adding 10 µL H2SO4 0.97% Fe 0x 40 Fe 1x Fe 4x Fe 8x Conversion efficiency (%) 30 20 10 0 30 60 Time (min) Figure 1.9 Degradation MB by different Fe2+ concentration in 60 minutes, pH = 2-3.5 The graph showed the degradation of MB by different Fe2+ concentration in 60 minutes With the increase concentration of Fe2+, the conversion efficiency increased It also increased with a rise of time, from to 60 minutes Within 60 minutes, conversion efficiency of MB was highest at 60 minutes and Fe 8x was 33 highest conversion efficiency with 41% at 60 minutes and Fe 0x was lowest at 1.4% 4.2 Determination the optimum concentration of H2O2 for degradation of MB To determine the optimum H2O2 concentration we used different H2O2 concentrations as following: treatment (H2O2 0.5x, M), treatment (H2O2 1x, 4.41×10−4 M), treatment (H2O2 2x, 8.82×10−4 M), treatment (H2O2 4x, 1.76×10−3 M), and treatment (H2O2 8x, 3.52×10−3 M) Those concentration have the same base concentration of MB, 3.13×10 −5 M and Fe2+ 2.86×10−4 M, respectively The pH was adjusted from 2-3.5 by adding 10 µL H2SO4 0.97% 45 40 35 Conversion Efficiency (%) 30 25 H2O2 0x 20 H2O2 0.5x H2O2 1x 15 H2O2 2x H2O2 4x 10 -5 10 20 30 40 50 60 TIme (min) Figure 2.1 Degradation MB by different [H2O2] concentration in 60 minutes, pH = 23.5 The graph presented the degradation of MB by different H2O2 concentration within 60 minutes With the increase concentration of H2O2, the conversion 34 efficiency increased It also increased with a rise of time, from to 60 minutes Within 60 minutes, conversion efficiency of MB was highest at 60 minutes and H2O2 4x was highest conversion efficiency with 41% at 60 minutes and H2O2 0.5x was lowest at 1.5% 4.3 Effect of pH value on degradation of MB To determine the effect of pH value on degradation of MB, experiments were conducted with treatments by base of [Fe2+], Fe 8x and [H2O2], H2O2 4x as following: treatment (pH 2.5-3.5), treatment (pH 4-5.5), treatment (pH 77.5) Conversion efficiency (%) 45 30 pH 2.5-3.5 pH 4.5-5 15 pH 7-7.5 0 30 60 Time (min) Figure 2.2 Effect of pH on degradation of MB The graph presented the degradation of MB by different pH value within 60 minutes Surprisingly, with the increase pH value, the conversion efficiency increased But the conversion efficiency still increased with a rise time, from to 60 minutes Within 60 minutes, conversion efficiency of MB was highest at 60 35 minutes The treatment 1, was adjusted pH 2-3.5, was highest conversion efficiency with 41% at 60 minutes Treatment 3, was adjusted pH 7, was lowest the conversion efficiency at 33 % 4.4 Degradation of MB by Iron (II), Iron (III) Both Fe3O4 magnetic nanoclusters and Au@FexOy nanocomposites have good catalytic potential on the degradation of methylene blue (Andre, 2014) In theory, the ratio between Fe (II) and Fe (III) reactants of Fe3O4 magnetic NPs was 0.5 As a result, Fe (II); Fe (III); Fe (II) + Fe (III) solution was considered to be our positive control which compared with our magnetic nanoclusters and Au@FexOy According to Figure 2.3, the decomposition of H2O2 reaction was rapid at the beginning when in the Fe (II) solution whereas decomposition of H2O2 was slightly slower Interestingly, the changed profile of the mixed Fe (II) and Fe (III) solution was similar approach to Fe (II) So, according to above observation, we assume that while the decomposition of MB start with Fe (III), other reaction may be involved during the decomposition reaction, which was shown below: Fe3+ + HO2• = Fe2+ + O2 + H+ (4) Fe2+ + HO2• + H+ = Fe3+ + H2O2 (5) 2HO2• = H2O2 + O2 (6) Although, the reaction was prior to Fe (II) for the degradation, still all the three groups achieve to 90 % The reaction was almost complete 36 100 Conversion efficiency (%) 80 60 Fe(II) 40 Fe(II) + Fe(III) Fe(III) 20 0 50 100 150 200 250 300 Time (min) Figure 2.3 Degradation of methylene blue by Fe (II); Fe (II) + Fe (III) and Fe (III) at pH 2.5-3.5 4.5 The use of MNC, Au@FexOy in degradation of dye 1) According to the optimum concentration of iron (II) and H2O2 as described in those experiments above, we apply to using magnetic nanocomposites in Fenton reaction for degradation of MB In the treatment, we used MNC with 2.86×10−4 M and H2O2, 1.76×10−3 M (4x), pH adjusted by adding 5µL NaOH in the solution The conversion efficiency was presented in Figure 2.4 37 100 H2O2 4x Conversion efficiency (%) 80 60 40 20 0 100 200 300 400 500 Time (min) Figure 2.4 Degradation of methylene blue by MNC, H2O2 4x and pH = From figure 2.4, degradation of MB by MNC with H2O2 4x, conversion efficiency is very low It became constant after 30 minutes The max concersion efficiency is 10% at 420 So the concentration of H2O2 here was not optimum for degradation of MB by magnetic nanoparticles 2) To verify the conversion ability of magnetic nanocomposites on degradation of dye, we conducted experiment with concentration of H2O2 at 200 times dilute fold for hours incubation Then, we further spike 20 µL H2O2 8.82 M in solutions to realize the degradation procedure 38 40 H2O2 200x Conversion efficiency (%) 30 Spike 20 10 0 150 300 450 600 750 Time (min) Figure 2.5 Degradation of methylene blue by MNC, H2O2 8.82×10−1 M (200x), pH = with spike at hours From the figure 2.5, when increase H2O2 concentration up to 200x, the conversion efficiency is still low and almost no reaction at 300 Surprisingly, after adding 20µL H2O2 8.82 M, conversion efficiency rapid increases tend to a 39% at 720 minutes This is a base for determination of H2O2 on MB degradation, we conduct experiment following 3) MNC and Au@FexOy was further investigated for MB degradation afterwards The experiments were conducted with MNC, Au@FexOy before annealing and Au@FexOy after annealing at the same concentration 2.86×10−4 M (Figure 2.6) The concentrations of H2O2 were kept at 8.82 M (2000 times diluted fold) 39 100 MNC Au@FexOy After ann Conversion efficiency (%) 80 Au@FexOy Before ann, 60 40 20 0 50 100 150 200 250 300 Time (min) Figure 2.6 Degradation of MB by MNC, Au@FexOy after annealing, Au@FexOy before annealing at pH = 7, [H2O2] = 2000x In figure 2.6, it showed that magnetic composite has well done reaction in the presence of H2O2 in Fenton reaction Maximum conversion efficiency of Au@FexOy after annealing, Au@FexOy before annealing and MNC are 80%, 23% and 71%, respectively We found that the behavior between Au@FexOy before and after through annealing process performed significantly different behaviors in degradation Surprisingly, the reaction was achieved almost 70-80 % in magnetic particles 4) To compare and assement the effectiveness between Iron ion and magnetic nanocomposites, experiments were conducted with treatments: - Treatment 1: H2O2 + H2O - Treatment 2: Fe2+ - Treatment 3: Fe3+ - Treatment 4: Fe 2++Fe3+ - Treatment 5: MNC, 2.86×10−4 M 40 - Treatment 6: Au@FexOy after annealing, 2.86×10−4 M - Treatment 7: Au@FexOy before anealing, 2.86×10−4 M 100 a) b) 80 c) Conversion efficiency (%) d) e) f) 60 g) 40 20 50 100 150 200 250 300 Time (min) Figure 2.7 Degradation of MB by a) H2O2 + H2O, b) Fe(II), c) Fe(III), d) Fe(II)+Fe(III), e) Au@FexOy after annealing, f) Au@FexOy before annealing and g) MNC (pH = 7) According to Figure 2.7, degradation of MB by Iron ion (II and III) group were rapid at the beginning of reaction with 90% conversion efficiency within 60 minnutes whereas groups from Au@FexOy, MNC was much slower when reaction began We found the precipitants from the magnetic particles in the bottom of plastic tubes after the experiments completed In detail, as we can see from Figure 2.8 (B), there were yellow precipitants on degradation of MB by Fe (II) This is evidence that Fe (II) is converted in to Fe (III) at the end of reaction On degradation of MB by magnetic nanocomposites, there are also precipitants at the end of reaction as present on Figure 2.8 (A) However, these are magnetic 41 nanoparticles after reaction and they still have magnetic field This is very important indicating advantages of using magnetic composites in Fenton’s reaction We can reuse or recycle them not only once use that presented in many studies with the benefit in reuse of magnetic nanoparticles (Han et al., 2014) Figure 2.8 Photos of A) degradation of MB by MNC at the beginning, a)-b) at the end of reaction and B) degradation of MB by Fe (II) at the end of reaction with concentration of 200 times dilute fold of H2O2 (pH = 7) after 12 hours In addition, even all the experiment for degradation of MB by magnetic nanoparticles were controlled with pH neutral (pH = 7) which was more suitable in real situation, the conversion efficiency was still remain certain extent compare to Iron (II)/Iron (III) Although the best condition for fenton reaction was conducted in pH 2.5-3.5 On the other hand, with core-shell nanostructure, probably because there was only an amount of Iron ion on surface of magnetic nanocomposites reacted with H2O2 in Fenton reaction; however, there was still iron ion inside non-react 42 In fact, when using Iron (II) or Iron (III) in Fenton’s reaction occurred in real wastewater environment, totally Iron ion will take part in the reaction However, Iron ions not only reacting with H2O2 same as in theory, it also reacts with ions or organic compounds in wastewater, this will affect to the conversion efficiency of degradation of dye By contrast, magnetic nanocomposites, will prevent nanoparticles and block organic compunds in wastewater react with iron ion This indicated the conversion efficiency of MNC and Au@FexOy lower than Iron (II)/Iron (III) but more realistic in the real cases 43 PART V DISCUSSION AND CONCLUSION 5.1 Discussion For degradation of methylene blue by Iron ions, the optimum concentrations of Iron ion, hydrogen peroxide were Fe 8x (2.86×10−4 M ) and H2O2 4x (1.76×10−3 M) was an optimum Fe2+ concentration for the most effective degradation of 3.13 × 10−5 M MB solution, the optimum pH value range from 24 For degradation of MB by magnetic nanocomposites, the optimum H2O2 concentration is 2000x (8.82×10−1 M) After hours, magnetic nanocomposites performed good in Fenton reaction for degradation of methylene blue with conversion efficiency of MNC at 71%, Au@FexOy after annealing at 80% and Au@FexOy before annealing at 23% 5.2 Conclusion Gold@iron oxide nanoparticles and magnectic nanoparticles were successfully synthesized by a simple and inexpensive 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for catalytic degradation of methylene blue Magnetic field was tentatively introduced into Fenton reactions system for the degradation. .. application for degradation of methylene blue 16 2.3.1 Fenton reaction 16 2.3.2 Fenton reaction for degradation of methylene blue 17 2.4 The use of magnetic nanocomposites in Fenton. .. nanocomposite to demonstrate the degradation of organic pollutants, a study: ? ?The use of magnetic nanocomposites in Fenton reaction for catalytic degradation of methylene blue" was conducted 1.2 Research’s